Acylation of aminopyridines and related compounds with endic anhydride

Article abstract of DOI:10.1007/s11178-005-0378-5

Reactions of bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboxanhydride (endic anhydride) with 2-, 3-, and 4-aminopyridines, 3-hydroxy- and 5-iodo-2-aminopyridines, 6-aminoquinoline, and 6-aminoquinoxaline involve chemoselective transformation of the exocyclic amino group. The resulting amido acids were converted into the corresponding carboximides, and the latter were epoxidated with peroxy acids. The structure of the products was confirmed by the IR, UV, and ¹H and ¹³C NMR spectra, as well as by calculation of the ¹H and ¹³C chemical shifts using the GIAO method (B3LYP/6-31G** approximation).

Full text of DOI:10.1007/s11178-005-0378-5

Russian Journal of Organic Chemistry, Vol. 41, No. 10, 2005, pp. 1530–1538. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 10, 2005,
pp. 1561–1570.
Original Russian Text Copyright © 2005 by L. Kas’yan, Tarabara, Pal’chikov, Krishchik, Isaev, A. Kas’yan.
Dedicated to Full Member of the Russian Academy of Sciences
N.S. Zefirov on His 70th Anniversary
Acylation of Aminopyridines and Related Compounds
with Endic Anhydride
L. I. Kas’yan1, I. N. Tarabara1, V. A. Pal’chikov1, O. V. Krishchik2,
A. K. Isaev3, and A. O. Kas’yan4
1 Dnepropetrovsk National University, per. Nauchnyi 13, Dnepropetrovsk, 49625 Ukraine
e-mail:cf@ff.dsu.dp.ua
2 Ukrainian State University of Chemical Technology, Dnepropetrovsk, Ukraine
3 Missisipi State University, Jackson, MS 39762, USA
4 Institut für organische Chemie, Rheinisch–Westfälische technische Hochschule, Aachen, Germany
Received May 23, 2005
Abstract—Reactions of bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboxanhydride (endic anhydride) with 2-,
3-, and 4-aminopyridines, 3-hydroxy- and 5-iodo-2-aminopyridines, 6-aminoquinoline, and 6-aminoquinoxa-
line involve chemoselective transformation of the exocyclic amino group. The resulting amido acids were
converted into the corresponding carboximides, and the latter were epoxidated with peroxy acids. The structure
of the products was confirmed by the IR, UV, and 1H and 13C NMR spectra, as well as by calculation of the 1H
and 13C chemical shifts using the GIAO method (B3LYP/6-31G** approximation).
Pinacidil (Ib) is a 4-aminopyridine derivative which is
known to activate potassium channels. Medical agents
on the basis of 2-aminopyridine are more widely
known; among these, antimicrobial agents Sulfidine
and Sulfasalazine, hypnotic agent Imovane, and
Suprastin (Ic) possessing antihistaminic and peripheral
anticholinergic activity [4].
Aromatic pyridine ring plays an important role in
metabolism of living organisms [1]. Pyridine deriva-
tive pyridoxine (vitamin B6) participates in one of the
main amino acid exchange processes, transamination
[2, 3], and pyridoxamine (Ia) is an intermediate prod-
uct in the synthesis of pyridoxine [4]. Pyridine ring
constitutes a structural fragment of alkaloids nicotine
and anabasine. 4-Aminopyridine affects peripheral
neuromediator processes and is used in medical prac-
tice for the treatment of residual muscle paralysis.
The present article reports on the reactions of bi-
cyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboxylic
(endic) anhydride (II) with aminopyridines IIIa–IIIe
and structurally related 6-aminoquinoline (IIIf) and
6-aminoquinoxaline (IIIg), subsequent transformation
of the adducts thus formed into the corresponding car-
boximides, and epoxidation of the latter with peroxy-
formic acid. The reactions were carried out under mild
conditions (in benzene at room temperature) to avoid
dehydration of amido acids IVa–IVg to give carbox-
imides Va–Vg [5] (Scheme 1). The structure of amines
IIIa–IIIg implies the possibility for their unusual
acylation and oxidation of imides Va–Vd which
contain additional nitrogen and oxygen nucleophilic
centers together with the double bond.
NCN Me
CH2NH2
CH2OH
HN
N
N
H
Bu-t
HO
Me
N
Ia
Ib
NMe2
N
N
O
O
· HCl
Cl
O
In fact, both 2- and 4-aminopyridines can exist as
two tautomers, the amino form being more stable.
Ic
II
1070-4280/05/4110-1530 © 2005 Pleiades Publishing, Inc.

ACYLATION OF AMINOPYRIDINES AND RELATED COMPOUNDS
1531
Scheme 1.
7
7
O
1
1
6
6
2
2
O
O
PhH, 20°C
AcOH, reflux
HCOOOH
RNH2
+
II
4
4
5
COOH
3
5
3
NR
NR
CONHR
O
O
IIIa–IIIg
IVa–IVg
Va–Vg
VIa, VIb, VId–Vg
R = 2-pyridyl (a), 3-pyridyl (b), 4-pyridyl (c), 3-hydroxy-2-pyridyl (d), 5-iodo-2-pyridyl (e), 6-quinolyl (f), 6-quinoxalyl (g).
According to Goldfarb et al. [6], there is no need of
considering the iminopyridine structure A as inter-
mediate in the formation of substituted iminopyridines
in the alkylation of aminopyridines (Scheme 2). Unlike
alkylation reactions whose regioselectivity depends on
pH [3], acetylation occurs mainly at the exocyclic
amino group [1, 7]; aminopyridines IIIa and IIIb react
with succinic anhydride just in that way [8]. The regio-
selectivity in the reactions of amines IIIa–IIIg with
endic anhydride was studied by spectral methods. The
IR and 1H NMR spectra of the aminolysis products did
not contradict the assumed structure of amido acids
IVa–IVg. In the IR spectra of these compounds we
plets, while 2-H and 3-H are coupled with each other
through a constant J of 8–10 Hz. The latter value
3
unambiguously indicates exo orientation of the 2-H
and 3-H protons and hence endo orientation of the
substituents on C2 and C3. Stereoisomeric structures
with exo,endo and endo,endo orientation of 2-H and
3-H are characterized by a considerably smaller vicinal
coupling constant (3J2,3 = 4–5 Hz). Protons at C2/C3,
C1/C4, and C5/C6 in compounds IVc and IVd are
equivalent in pairs. Protons of the methylene bridge,
syn-7-H and anti-7-H in the spectra of all compounds
resonate as doublets at į 1.20–1.35 ppm with a coupl-
ing constant of 9–10 Hz. In addition, signals from the
amide NH proton and from protons in the pyridine ring
(į 7.03–8.20 ppm) were present.
The UV spectra of compounds IIIa, IIIb, IVa, IVb,
Va, and Vb are consistent with their structure and, in
keeping with the data of [6] (where the reactivity of
aminopyridines was studied), indicate that compounds
III exist mainly in the amino form and that their
reactions with electrophiles involve the exocyclic
nitrogen atom.
The observed regioselectivity follows from the
electron density distribution in molecules IIIa–IIIg,
which was determined previously (in 1970s) for some
compounds of this series. Table 1 contains proton
affinities of the nitrogen atoms in compounds IIIa–
IIIg, which were calculated by the PM3 semiempirical
method [11]. In all compounds, except for IIId, the
proton affinities of the endocyclic nitrogen atoms are
greater than those of the amino nitrogen atom. The
smallest difference was found for 2-aminopyridine and
2-amino-5-iodopyridine (2.3 kcal/mol), and the largest,
for 4-aminopyridine (14.0 kcal/mol). The proton affin-
observed absorption bands at 1585–1570 (įN–H
,
amide II) and 1265–1255 cm–1 (ȞC–N, amide III) [9].
Each compound IVa–IVg showed in the spectrum
a distinct absorption band at 3370–3250 cm–1 due to
N–H stretching vibrations and carbonyl absorption
band of the carboxy group at 1720–1710 cm–1. The
amide carbonyl stretching vibration band was overlap-
ped by absorption of C=N bonds in the heterocyclic
fragment (1655–1635 cm–1) [9]. Absorption bands
belonging to the unsaturated norbornene fragment
were generally obscured by absorption of aromatic
C=C bonds. A characteristic band is observed at 725–
710 cm–1; it originates from bending vibrations of the
=C–H bond at the strained double C=C bond [10].
The 1H NMR spectra of compounds IVa, IVb, IVe,
and IVg contained multiplets from the nonequivalent
5-H and 6-H protons in the olefinic fragment (į 6.05–
6.20 ppm). Signals from the bridgehead 1-H and 4-H
protons and exo-2-H and exo-3-H were located in
a stronger field. These signals can readily be distin-
guished: the bridgehead protons give unresolved multi-
Scheme 2.
N
NH2
N
NH2
N
NH
N
NH
H
H
A
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

KAS’YAN et al.
1532
Table 1. Energy parameters of occupied molecular orbitals and orbital coefficientsa in molecules IIIa–IIIg (PM3
calculations)
Proton affinity,
kcal/mol
N1
NH2
HOMO
II-OMO
Comp.
no.
E, eV
orbital coefficients, %
E, eV
orbital coefficients, %
199.8 197.5 –8.833 7.63 (N1), 8.55 (C2), 15.65 (C3), 19.39 –10.284 72.78 (N1), 6.42 (C2), 5.29 (C5)
IIIa
IIIb
IIIc
(C5), 41.89 (NH2)
202.3 194.6 –8.896 13.47 (C2), 12.30 (C3), 9.04 (C4), 17.13 –10.119 73.96 (N1), 5.16 (C2), 5.53 (C5)
(C6), 41.34 (NH2)
205.9 191.9 –9.103 15.66 (N1), 12.65 (C3), 9.62 (C4), 12.64 –10.071 23.42 (C2), 26.58 (C3), 26.60
(C5), 45.21 (NH2)
(C5), 23.41 (C6) [75.42 (N1) in
III-OMO (–10.110)]
200.7 203.4 –8.971 14.06 (C2), 18.36 (C3), 13.53 (C5), 10.58 –10.120 25.67 (N1), 12.87 (NH2), 8.79
IIId
IIIe
(C6), 31.36 (NH2), 6.73 (O)
(O), 9.34 (C3), 27.21 (C4), 10.65
(C6) [72.77 (N1) in IV-OMO
(–10.433)]
199.3 197.0 –8.685 33.61 (I), 5.01 (N1), 14.09 (C5), 7.06 0–9.405 97.47 (I )[57.26 (I), 25.32 (NH2)
(C2), 9.01 (C3), 23.77 (NH2)
in III-OMO (–9.686)] [72.36
(N1) in IV-OMO (–10.467)]
206.8 199.1 –8.591 5.07 (C4), 12.47 (C5), 21.16 (C6), 5.05 0–9.412 7.60 (N1), 25.13 (C4), 19.33 (C9),
IIIf
(C8), 8.01 (C10), 30.23 (NH2)
12.67 (C3) [72.06 (N1) in
III-OMO (–10.118)]
199.5, 196.9 –8.777 7.57 (C2), 20.76 (C6), 11.69 (C7), 11.75 0–9.716 27.46 (C8), 17.17 (C9), 15.02 (C5),
IIIg
200.2
(C10), 34.17 (NH2)
11.63 (C6), 13.78 (C3), 5.16 (N1),
5.39 (N4) [34.79 (N1), 34.53
(N4) in III-OMO (–9.993)]
a
NH2 stands for the amino nitrogen atom.
ity of the oxygen atom in the hydroxy group of IIId is
considerably lower (153.9 kcal/mol), as compared to
the nitrogen atoms. Analysis of the charge distribution
also indicates negative charge localization on the
pyridine nitrogen atoms. Isomeric aminopyridines are
characterized by fairly similar charges on the exocyclic
nitrogen atom (0.08–0.09 a.u.); the charges on the ring
nitrogen atom are considerably greater, but they differ
only slightly for 2- and 4-aminopyridines. The largest
negative charge is localized on the hydroxy oxygen
atom in molecule IVd.
nitrogen atom contributes most to the II-OMO (73–
74% for 2- and 3-aminopyridines), III-OMO (4-amino-
pyridine and compounds IIIf and IIIg), and IV-OMO
(IIId, IIIe). The contribution of the ring nitrogen atom
to the HOMO of 2- and 4-aminopyridines is small
(7.63 and 15.66%, respectively), and the HOMO of
3-aminopyridine contains no contribution of N1.
We can conclude that the ring nitrogen atom in
aminopyridines is characterized by increased proton
affinity and the maximal negative charge and that the
amino nitrogen atom provides the largest contribution
to the HOMO, which is the crucial factor in primary
overlap of frontier orbitals of the reagents. Presumably,
the examined reactions of aminopyridines with endic
anhydride are orbital-controlled.
Amido acids IVa–IVg were converted into the cor-
responding carboximides by heating in boiling acetic
acid. The progress of the reactions was monitored by
TLC. The IR spectra of imides Va–Vg contained
absorption bands due to symmetric and antisymmetric
stretching vibrations of the carbonyl groups (1785–
1775 and 1730–1706 cm–1), the low-frequency band
In addition, Table 1 contains the calculated energies
of occupied molecular orbitals and the corresponding
orbital coefficients of some atoms in molecules IIIa–
IIIg. The highest occupied molecular orbital (HOMO)
in all these compounds is localized on the amino group
(23.77–45.21%); the contribution of the later is the
largest in aminopyridine molecules (41.34–45.21%),
and the smallest, in 2-amino-5-iodopyridine (IIIe). The
iodine atom in the latter is characterized by orbital co-
efficients of 33.61, 97.47, and 57.26% in the HOMO,
II-OMO, and III-OMO, respectively. The endocyclic
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

ACYLATION OF AMINOPYRIDINES AND RELATED COMPOUNDS
1533
1
Table 2. H and 13C chemical shifts in the NMR spectra of
compounds IVa, Va, Vc, and VIa, calculated by the GIAO
method (B3LYP/6-31G** approximation)
being appreciably stronger [9]. Imides having hetero-
aromatic =C–H bonds and unsaturated fragments gave
rise to absorption in the regions 1515–1510 and 850–
720 cm–1. Stretching vibrations of the strained double
C=C bond (1575–1550 cm–1) were not observed
because of high molecular symmetry [10].
Chemical shifts į or įC, ppm
Atom
IVa
Va
Vc
VIa
N1
003.4
003.9
003.7
003.0
006.8
006.9
001.8
001.4
049.8
055.1
057.6
048.4
132.5
132.3
053.6
003.3
003.1
003.2
003.3
006.5
006.5
001.7
001.4
049.2
049.1
049.2
048.9
132.6
131.3
049.1
003.3
003.1
003.1
003.4
006.6
006.5
001.7
001.4
049.6
048.6
048.6
049.8
131.8
132.1
053.7
002.9
002.9
003.0
002.8
003.1
003.1
001.8
000.8
044.0
049.7
049.7
043.7
048.8
048.8
032.0
1
The H NMR spectra of imides Va–Vg are fairly
N2
simple due to high molecular symmetry. The olefinic
protons 5-H and 6-H in Va–Vg are deshielded as com-
pared to those in norbornene (ǻį = 0.2–0.3 ppm) due
to the presence of two electron-acceptor substituents in
the bicyclic fragment; their chemical shifts are similar
to the chemical shifts of the corresponding protons in
endic anhydride (į 6.32 and 6.30 ppm). Higher electro-
negativity of the anhydride moiety, as compared to
imide, is reflected primarily in the position of signals
from 2-H and 3-H, and also of the bridgehead 1-H and
3-H
4-H
5-H
6-H
syn-7-H
anti-7-H
C1
C2
C3
1
4-H protons. In the H NMR spectra of imides V we
C4
observed no coupling between 2-H and 3-H; therefore,
considerable difficulties were encountered while dis-
tinguishing between their signals and those of the
bridgehead protons. The signals were assigned on the
basis of the results of quantum-chemical calculations
C5
C6
C7
1
13
of H and C chemical shifts (Table 2), which were
performed for compounds IVa, Va, Vc, and VIa by the
GIAO (B3LYP/6-31G**) method [12]. According to
the calculations, the 2-H/3-H and C2/C3 signals of
compounds IVa and VIa should appear in a weaker
field relative to the 1-H/4-H and C1/C4 signals, respec-
tively, while the corresponding signals of imides Va
and Vc should be arranged in the reverse order.
sumably, the following two factors are responsible for
the observed chemoselectivity in the oxidation of
imides V with peroxyformic acid. The first of these is
strained character of the double bond [10], and the
second is protonation of the highly basic pyridine
nitrogen atoms with excess formic acid.
In order to estimate the chemoselectivity in the
oxidation of imide Va we calculated the energy and
structure of its occupied molecular orbitals by the PM3
method [11]. The results showed that the highest
molecular orbital in Va is localized by 87% on the
C5 and C6 atoms; obviously, this is the reason why
peroxy acids react at the double bond to give oxirane
derivative.
Carboximides V were subjected to epoxidation at
the strained double bond by treatment with peroxy-
formic acid which was used previously for oxidation of
other carboximides [13]. Peroxyformic acid was pre-
pared in situ from 98% formic acid and 50% hydrogen
peroxide. In all cases, successful application of
peroxyformic acid was ensured by its high acidity and
reactivity as electrophile and oxidant, as well as by
specific properties of the imide substrates having two
electron-acceptor substituents which appreciably
reduce nucleophilic reactivity of unsaturated com-
pounds. These substituents destabilize intermediate
cationic species, thus preventing rearrangement proc-
ess which could accompany reactions of olefins with
peroxyformic acid [14]. Despite the presence of
oxygen and nitrogen nucleophilic centers, reactions of
imides Va, Vb, and Vd–Vg with peroxyformic acid
involved only the olefinic double bond, and the oxida-
tion products were epoxy derivatives VIa, VIb, and
VId–VIg which were isolated in 47–81% yield. Pre-
The structure of the oxidation products was con-
1
firmed by the IR and H and 13C NMR data. The IR
spectrum of VIa, as well as of the other imide deriva-
tives, contained carbonyl absorption bands at 1770 and
1720 cm–1 and a characteristic band at 850 cm–1 due to
stretching vibrations of the oxirane C–O bond [15].
Like parent imides, epoxy derivatives VI are charac-
terized by a high molecular symmetry which com-
1
plicates signal assignment in their H and 13C NMR
spectra. The spectra were analyzed with the use of
quantum-chemical calculation data (Table 2). Unlike
imides Va and Vb, the 5-H and 6-H protons resonate in
a stronger field (į 3.30 ppm), and signals from the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

KAS’YAN et al.
1534
Scheme 3.
COOOH
COOH
8
N
HO
O
1
2
9
O
O
7
Na2CO3, H2O
3
N
N
NH
6
O4
5
N
N
O
O
O
O
Va
VIa
VII
other protons in the bicyclic skeleton are also displaced
upfield. The same also applies to protons of the
bridging methylene group, syn-7-H and anti-7-H; the
difference in the chemical shifts between the latter
increases in going from imides Va and Vb to epoxy
derivatives VIa and VIb. The anti-7-H signal is dis-
placed upfield due to magnetically anisotropic prop-
erties of the oxirane ring (this proton is located directly
above the oxirane ring plane). Considerable nonequiv-
alence of the 7-H protons together with upfield shift of
the signal from one of these indicates exo orientation
of the epoxy fragment. The positions of signals from
the pyridine fragment did not change. This means that
this fragment was not involved in oxidation with per-
oxyformic acid. Otherwise (in the case of formation
of NĺO group), the corresponding signals should be
displaced downfield.
hydride VIII with 2-aminopyridine (IIIa) according to
the procedure described in [17] (Scheme 4). In the IR
spectrum of lactone VII we observed absorption bands
at 3440, 1779, 1689, 1530, and 1256 cm–1 due to vibra-
tions of the hydroxy group, lactone carbonyl group,
amide carbonyl group, N–H bond (bending vibrations),
and amide C–N bond, respectively [9].
Scheme 4.
O
O
PhH, 20°C
+
VII
O
N
NH2
O
VIII
1
Unlike epoxy imide VIa, the H NMR spectrum of
hydroxy lactone VII contained no signals in the region
of į 3.30 ppm (oxirane ring protons) but contained
a signal at į 5.15 ppm from the hydroxy proton and
two quite characteristic signals, a doublet at į 4.35 ppm
(3J3,7 = 4.4 Hz) and a singlet at į 4.24 ppm, which
belong to 3-H and 2-H, respectively.
13
By analysis of the C NMR spectra we succeeded
in distinguishing between imide Va, on the one hand,
and amido acid IVa and epoxy derivative VIa, on the
13
other. The C NMR spectra of isomeric carboximides
Va and Vb were fairly similar. Amido acid IVa dis-
played signals from nonequivalent carbonyl carbon
atoms and C5 and C6. In the spectrum of VIa, the
C5 and C6 signals appeared in a stronger field
(įC 48.9 ppm); the bridging carbon signal (C7) was
also displaced upfield (įC 29.3 ppm) relative to the
corresponding signal of imide Va. These data are con-
sistent with published data for other substituted epoxy-
norbornanes [16].
Analogous reactions of amido acids were not the
subject of a special study. Epoxidation of amido acid
IVa with peroxyformic acid at 0°C gave a mixture of
lactone VII and 2-pyridylammonium salt IX, the latter
prevailing (according to the 1H NMR data; Scheme 5).
The corresponding tricyclic acid was reported pre-
viously. We failed to separate the product mixture into
individual compounds, for its components were poorly
soluble in most organic solvents but readily soluble
in water.
In the epoxidation of N-(2-pyridyl)bicyclo[2.2.1]-
hept-5-ene-endo-2,endo-3-dicarboximide (Va) with
monoperoxyphthalic acid (generated in situ from
phthalic anhydride and 35%hydrogen peroxide) we
isolated different products, depending on the mode of
treatment of the reaction mixture. Column chromatog-
raphy on aluminum oxide afforded epoxy imide VIa,
while treatment of the mixture with a solution of
sodium carbonate gave an unexpected product,
hydroxy lactone VII (Scheme 3). Compound VII was
obtained by us previously by reaction of epoxy an-
1
Despite general similarity, the H NMR spectra of
VII and IX show some differences: signal of the am-
monium protons in IX appears at į 8.16 ppm against
į 10.64 ppm for the amide proton in VII, and all
signals in the spectrum of salt IX are displaced upfield
relative to those of amido lactone VII. Presumably, the
carboxy and carboxamide groups in amido acid IVa
compete with each other in the intramolecular cy-
clization of intermediate epoxy derivative.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

ACYLATION OF AMINOPYRIDINES AND RELATED COMPOUNDS
1535
Scheme 5.
O
N
HO
COOH
NH
COOH
NH
HCOOOH, 0°C
O
O
NH
O
O
O
N
N
IVa
VII, 29%
HO
+
COO
N
NH3
O
O
IX, 71%
EXPERIMENTAL
10.32 s (1H, NH); 8.26, 7.96, 7.78, 7.02 (4H, Harom);
3
3
6.17 m (1H, 5-H); 6.06 m (1H, 6-H, J5,6 = 5.5, J4,5
=
3J6,1 = 3.1 Hz); 3.49 m (1H, 2-H); 3.24 m (1H, 3-H,
The IR spectra were recorded on UR-20 and
Specord 75IR spectrometers from samples prepared as
KBr pellets. The UV spectra were measured in the
Ȝ range from 200 to 350 nm on a Specord UV-Vis
spectrophotometer from solutions in ethanol (c =
10–4 M, d = 1 cm). The 1H NMR spectra were obtained
on Varian VXR (200 or 300 MHz) and Inova 400
instruments (400 MHz) from solutions in DMSO-d6
3
3
3J2,3 = 10.4, J2,1 = J3,4 = 3.2 Hz); 3.07 m (1H, 1-H);
3.01 m (1H, 4-H); 1.18 d (1H, syn-7-H); 1.17 d (1H,
2
13
anti-7-H, J7,7 = 8.4 Hz). C NMR spectrum, įC, ppm:
178.9 (C=O), 178.8 (C=O), 135.9 (C5, C6), 51.4 (C7),
46.3 (C1, C4), 46.0 (C2), 45.9 (C3). Found, %: C 65.14;
H 5.46; N 10.81. C14H14N2O3. Calculated, %: C 65.12;
H 5.43; N 10.85.
13
and CD3OD using TMS as internal reference. The C
endo-3-(3-Pyridylcarbamoyl)bicyclo[2.2.1]hept-
5-ene-endo-2-carboxylic acid (IVb). Yield 4.36 g
(84%), mp 187–189°C. IR spectrum, Ȟ, cm–1: 3276,
3130, 3038, 1710, 1690, 1588, 1422, 1334, 1252, 702.
UV spectrum, Ȝmax, nm (logİ): 246 (4.15), 286 (3.54).
1H NMR spectrum, į, ppm: 11.60 s (1H, COOH); 9.90 s
(1H, NH); 8.65, 8.20, 7.90, 7.25 (4H, Harom); 6.18 m
(1H, 5-H); 6.08 m (1H, 6-H); 3.48 m (1H, 2-H);
3.27 m (1H, 3-H); 3.09 m (1H, 1-H); 3.02 m (1H,
4-H); 1.35 d (1H, syn-7-H); 1.22 d (1H, anti-7-H).
Found, %: C 65.05; H 5.48; N 10.91. C14H14N2O3. Cal-
culated, %: C 65.12; H 5.43; N 10.85.
NMR spectra were measured on an Inova 400 spec-
trometer at 100.57 MHz. The progress of reactions and
the purity of products were monitored by TLC on
Silufol UV-254 plates using diethyl ether and 2-pro-
panol as eluent; spots were visualized by treatment
with iodine vapor. The elemental compositions were
determined on a Carlo Erba analyzer.
Reaction of bicyclo[2.2.1]hept-5-ene-endo-
2,endo-3-dicarboxylic anhydride (II) with amines
IIIa–IIIg (general procedure). Amine IIIa–IIIg,
0.02 mol, was added under stirring to a solution of
3.28 g (0.02 mol) of anhydride II in 10–15 ml of
anhydrous benzene, and the mixture was stirred at
room temperature until the reaction was complete
(TLC). The precipitate was filtered off, washed with
benzene on a filter, and dried in air.
endo-3-(4-Pyridylcarbamoyl)bicyclo[2.2.1]hept-
5-ene-endo-2-carboxylic acid (IVc). Yield 2.58 g
(50%), mp 195–197°C. IR spectrum, Ȟ, cm–1: 3352,
3178, 3030, 1730, 1640, 1586, 1438, 1338, 1276, 832,
726. 1H NMR spectrum, į, ppm: 10.31 s (1H, COOH),
7.99 and 6.51 (4H, Harom), 6.33 s (1H, NH), 6.08 m
(2H, 5-H, 6-H), 3.12 m (2H, 2-H, 3-H), 3.00 m (2H,
1-H, 4-H), 1.24 d (1H, syn-7-H), 1.15 d (1H, anti-7-H,
2J7,7 = 8.4 Hz). Found, %: C 65.20; N 5.39; N 10.90.
C14H14N2O3. Calculated, %: C 65.12; N 5.43; N 10.85.
endo-3-(2-Pyridylcarbamoyl)bicyclo[2.2.1]hept-
5-ene-endo-2-carboxylic acid (IVa). Yield 4.46 g
(86%), mp 147–149°C. IR spectrum, Ȟ, cm–1: 3210,
3130, 3034, 1710, 1680, 1582, 1434, 1334, 1252, 722.
UV spectrum, Ȝmax, nm (logİ): 243 (4.23), 283 (3.93).
1H NMR spectrum, į, ppm: 11.68 s (1H, COOH);
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

KAS’YAN et al.
1536
endo-3-(3-Hydroxy-2-pyridylcarbamoyl)bicyclo-
N-(2-Pyridyl)bicyclo[2.2.1]hept-5-ene-endo-
2,endo-3-dicarboximide (Va). Yield 0.38 g (80%),
mp 171–173°C. IR spectrum, Ȟ, cm–1: 3039, 1776,
[2.2.1]hept-5-ene-endo-2-carboxylic acid (IVd).
Yield 3.29 g (60%), mp 154–156°C. IR spectrum, Ȟ,
cm–1: 3425, 3325, 3020, 1695, 1640, 1590, 1425, 1380,
1270, 740. 1H NMR spectrum, į, ppm: 7.35, 6.80, 6.35
(3H, Harom); 6.10 m (2H, 5-H, 6-H); 5.10 s (1H, OH);
3.12 m (2H, 2-H, 3-H); 3.03 m (2H, 1-H, 4-H); 1.35 d
(1H, syn-7-H); 1.28 d (1H, anti-7-H, 2J7,7 = 9.7 Hz).
Found, %: C 61.39; H 5.10; N 10.33. C14H14N2O4. Cal-
culated, %: C 61.31; H 5.11; N 10.22.
1704, 1487, 1338, 1176, 845, 705. UV spectrum, Ȝmax
,
1
nm (logİ): 227 (4.16), 267 (3.78). H NMR spectrum,
į, ppm: 8.58, 8.36, 7.61, 7.52 (4H, Harom); 6.26 m
(2H, 5-H, 6-H); 3.54 m (2H, 1-H, 4-H); 3.35 m (2H,
13
2-H, 3-H); 1.61 m (2H, syn-7-H, anti-7-H). C NMR
spectrum, įC, ppm: 177.1 (C=O); 149.7, 148.2, 135.4,
129.6, 124.6 (Carom); 135.2 (C5, C6); 52.5 (C7); 46.4
(C1, C4); 45.6 (C2, C3). Found, %: C 69.91; H 5.08;
N 11.71. C14H12N2O2. Calculated, %: C 70.00; H 5.00;
N 11.67.
endo-3-(5-Iodo-2-pyridylcarbamoyl)bicyclo-
[2.2.1]hept-5-ene-endo-2-carboxylic acid (IVe). Yield
6.80 g (89%), mp 219–220°C. IR spectrum, Ȟ, cm–1:
3250, 3045, 1722, 1710, 1612, 1585, 1545, 1482,
N-(3-Pyridyl)bicyclo[2.2.1]hept-5-ene-endo-
2,endo-3-dicarboximide (Vb). Yield 0.34 g (71%),
mp 167–169°C. IR spectrum, Ȟ, cm–1: 3458, 3040,
1776, 1706, 1378, 1177, 706. UV spectrum: Ȝmax 265 nm
1
1380, 1192, 1020, 740. H NMR spectrum, į, ppm:
11.70 s (1H, COOH); 10.50 s (1H, NH); 8.48, 8.03,
7.85 (3H, Harom); 6.15 m (1H, 5-H); 6.07 m (1H, 6-H,
3
3
1
3J5,6 = 5.6, J4,5 = J6,1 = 2.4 Hz); 3.48 m (1H, 2-H);
(logİ 3.51). H NMR spectrum, į, ppm: 8.51, 8.36,
3
3
3
3.42 m (1H, 3-H, J2,3 = 10.4, J2,1 = J3,4 = 3.3 Hz);
3.27 m (1H, 1-H); 3.22 m (1H, 4-H); 1.30 d (1H, syn-
7-H); 1.25 d (1H, anti-7-H, J7,7 = 8.6 Hz). Found, %:
7.67, 7.50 (4H, Harom); 6.25 m (2H, 5-H, 6-H); 3.53 m
(2H, 1-H, 4-H); 3.40 m (2H, 2-H, 3-H); 1.73 d
2
2
(1H, syn-7-H); 1.65 d (1H, anti-7-H, J7,7 = 8.7 Hz).
C 43.69; H 3.45; N 7.35. C14H13IN2O3. Calculated, %:
C 43.75; H 3.39; N 7.29.
13C NMR spectrum, įC, ppm: 177.1 (C=O); 148.5,
147.0, 135.3, 129.7, 124.2 (Carom); 134.6 (C5, C6); 52.1
(C7); 46.2 (C1, C4); 45.6 (C2, C3). Found, %: C 70.06;
H 5.03; N 11.61. C14H12N2O2. Calculated, %: C 70.00;
H 5.00; N 11.67.
endo-3-(6-Quinolylcarbamoyl)bicyclo[2.2.1]hept-
5-ene-endo-2-carboxylic acid (IVf). Yield 5.78 g
(94%), mp 195–197°C. IR spectrum, Ȟ, cm–1: 3295,
3160, 3010, 1710, 1645, 1570, 1530, 1370, 1275,
1220, 720. Found, %: C 70.04; H 5.15; N 10.01.
C18H16N2O3. Calculated, %: C 70.13; H 5.19; N 9.09.
N-(4-Pyridyl)bicyclo[2.2.1]hept-5-ene-endo-
2,endo-3-dicarboximide (Vc). Yield 0.38 g (80%),
mp 150–152°C. IR spectrum, Ȟ, cm–1: 1785, 1715,
1
1515, 1350, 1180, 720. H NMR spectrum, į, ppm:
endo-3-(6-Quinoxalylcarbamoyl)bicyclo[2.2.1]-
hept-5-ene-endo-2-carboxylic acid (IVg). Yield
6.01 g (97%), mp 161–162°C. IR spectrum, Ȟ, cm–1:
3312, 3285, 3020, 1725, 1710, 1635, 1600, 1560,
8.02 and 6.63 (4H, Harom), 6.10 m (2H, 5-H, 6-H),
3.10 m (2H, 1-H, 4-H), 3.05 m (2H, 2-H, 3-H), 1.28 d
(1H, syn-7-H); 1.20 d (1H, anti-7-H). Found, %:
C 70.08; H 4.96; N 11.65. C14H12N2O2. Calculated, %:
C 70.00; H 5.00; N 11.67.
1
1520, 1440, 1265, 1210, 1048, 720. H NMR spec-
trum, į, ppm: 11.73 s (1H, COOH); 8.85, 8.77, 8.43
(3H, Harom); 8.31 s (1H, NH); 8.00, 7.86 (2H, Harom);
6.23 m (1H, 5-H); 6.11 m (1H, 6-H); 3.46 m (1H,
2-H); 3.43 m (1H, 3-H); 3.14 m (1H, 1-H); 3.05 m
(1H, 4-H); 1.38 d (1H, syn-7-H); 1.31 d (1H, anti-7-H,
2J7,7 = 6.8 Hz). Found, %: C 66.10; H 4.91; N 13.50.
C17H15N3O3. Calculated, %: C 66.02; H 4.85; N 13.59.
N-(3-Hydroxy-2-pyridyl)bicyclo[2.2.1]hept-5-
ene-endo-2,endo-3-dicarboximide (Vd). Yield 0.33 g
(65%), mp 269–271°C. IR spectrum, Ȟ, cm–1: 3040,
1785, 1730, 1595, 1480, 1395, 1350, 1200, 1175, 730.
1H NMR spectrum, į, ppm: 9.85 s (1H, OH); 7.90,
7.26, 7.18 (3H, Harom); 6.18 m (2H, 5-H, 6-H); 3.42 m
(2H, 1-H, 4-H); 3.35 m (2H, 2-H, 3-H); 1.68 d (1H,
Bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicar-
boximides Va–Vg (general procedure). A solution of
2 mmol of amido acid IVa–IVg in 10–15 ml of glacial
acetic acid was heated under reflux until the reaction
was complete (6–10 h, TLC). The solvent was re-
moved under reduced pressure, 5–7 ml of water was
added to the residue, and the precipitate was filtered
off, dried, and recrystallized from 2-propanol.
2
syn-7-H); 1.60 d (1H, anti-7-H, J7,7 = 8.0 Hz). Found,
%: C 65.71; H 4.73; N 11.06. C14H12N2O3. Calculated,
%: C 65.63; H 4.69; N 10.94.
N-(5-Iodo-2-pyridyl)bicyclo[2.2.1]hept-5-ene-
endo-2,endo-3-dicarboximide (Ve). Yield 0.40 g
(54%), mp 156–157°C. IR spectrum, Ȟ, cm–1: 3015,
1790, 1730, 1580, 1475, 1390, 1350, 1190, 745.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

ACYLATION OF AMINOPYRIDINES AND RELATED COMPOUNDS
1537
Yield 0.26 g (47%), mp 286–288°C (decomp.). IR
Found, %: C 45.95; H 2.99; N 7.59. C14H11 IN2O2. Cal-
culated, %: C 45.90; H 3.01; N 7.65.
spectrum, Ȟ, cm–1: 3050, 1792, 1732, 1585, 1480,
1
1320, 1205, 1190, 865. H NMR spectrum, į, ppm:
N-(6-Quinolyl)bicyclo[2.2.1]hept-5-ene-endo-
2,endo-3-dicarboximide (Vf). Yield 0.54 g (93%),
mp 209–211°C. IR spectrum, Ȟ, cm–1: 3020, 1785,
1730, 1518, 1390, 1190, 725. Found, %: C 74.55;
H 4.94; N 9.72. C18H14N2O2. Calculated, %: C 74.48;
H 4.83; N 9.66.
8.00 s (1H, OH), 7.35 (3H, Harom), 3.21 m (2H, 5-H,
6-H), 2.95 m (2H, 2-H, 3-H), 2.95 m (2H, 1-H, 4-H),
2
1.40 d (1H, syn-7-H), 1.11 d (1H, anti-7-H, J7,7
=
9.1 Hz). Found, %: C 61.82; H 4.46; N 10.41.
C14H12N2O4. Calculated, %: C 61.76; H 4.41; N 10.29.
exo-5,6-Epoxy-N-(5-iodo-2-pyridyl)bicyclo-
[2.2.1]heptane-endo-2,endo-3-dicarboximide (VIe).
Yield 0.44 g (58%), mp 148–150°C (decomp.). IR
spectrum, Ȟ, cm–1: 3060, 1778, 1712, 1566, 1462,
1362, 1190, 848. Found, %: C 44.03; H 2.90; N 7.37.
C14H11IN2O3. Calculated, %: C 43.98; H 2.88; N 7.33.
N-(6-Quinoxalyl)bicyclo[2.2.1]hept-5-ene-endo-
2,endo-3-dicarboximide (Vg). Yield 0.43 g (75%),
mp 226.5–228°C. IR spectrum, Ȟ, cm–1: 3025, 1780,
1722, 1515, 1392, 1195, 728. Found, %: C 70.03;
H 4.51; N 14.38. C17H13N3O2. Calculated, %: C 70.10;
H 4.47; N 14.43.
Oxidation of bicyclo[2.2.1]hept-5-ene-endo-
2,endo-3-dicarboximides Va, Vb, and Vd–Vg with
peroxyformic acid (general procedure). Bicyclo-
[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximide Va,
Vb, or Vd–Vg, 2 mmol, was dissolved in 8–10 ml of
98% formic acid, 4 mmol of 50% hydrogen peroxide
was added dropwise under stirring, and the mixture
was stirred at room temperature until the reaction was
complete (3–7 days, TLC). Volatile compounds were
removed under reduced pressure, and the residue was
purified by recrystallization from 2-propanol or ethyl
acetate.
exo-5,6-Epoxy-N-(6-quinolyl)bicyclo[2.2.1]hept-
ane-endo-2,endo-3-dicarboximide (VIf). Yield 0.50 g
(81%), mp 243–244°C. IR spectrum, Ȟ, cm–1: 3052,
1
1768, 1712, 1502, 1372, 1176, 854. H NMR spec-
trum, į, ppm: 8.98, 8.42, 8.12, 7.99, 7.66, 7.60 (6H,
Harom); 3.48 m (2H, 5-H, 6-H); 3.41 m (2H, 2-H, 3-H);
3.01 m (2H, 1-H, 4-H); 1.45 d (1H, syn-7-H); 1.17 d
2
(1H, anti-7-H, J7,7 = 10.2 Hz). Found, %: C 70.51;
H 4.60; N 9.21. C18H14N2O3. Calculated, %: C 70.59;
H 4.58; N 9.15.
exo-5,6-Epoxy-N-(6-quinoxalyl)bicyclo[2.2.1]-
heptane-endo-2,endo-3-dicarboximide (VIg). Yield
0.47 g (76%), mp 248–250°C (decomp.). IR spectrum,
Ȟ, cm–1: 3070, 1770, 1712, 1504, 1380, 1180, 844.
Found, %: C 66.52; H 4.31; N 13.60. C17H13N3O3. Cal-
culated, %: C 66.45; H 4.23; N 13.68.
exo-5,6-Epoxy-N-(2-pyridyl)bicyclo[2.2.1]hept-
ane-endo-2,endo-3-dicarboximide (VIa). Yield 0.37 g
(71%), mp 176–178°C. IR spectrum, Ȟ, cm–1: 3040,
1
1770, 1720, 1500, 1370, 850. H NMR spectrum, į,
ppm: 8.38 (1H, Harom), 7.54 (1H, Harom), 7.46 (1H,
Harom), 3.39 m (2H, 5-H, 6-H), 2.98 m (2H, 2-H, 3-H),
2.30 m (2H, 1-H, 4-H), 1.41 d (1H, syn-7-H), 1.15 d
Oxidation of compound Va with monoperoxy-
phthalic acid. a. A 35% solution of hydrogen per-
oxide, 0.43 g (4.4 mmol), was added under stirring to
a mixture of 0.53 g (2.2 mmol) of compound Va,
0.65 g (4.4 mmol) of phthalic anhydride, and 0.07 g
(1.1 mmol) of urea in 20 ml of ethyl acetate. The mix-
ture was stirred at room temperature until the reaction
was complete (TLC) and was then passed through
a column charged with aluminum oxide. The solvent
was removed under reduced pressure, and the residue
was recrystallized from 2-propanol. We thus isolated
0.34 g (60%) of compound VIa.
2
13
(1H, anti-7-H, J7,7 = 10.0 Hz). C NMR spectrum, įC,
ppm: 175.2 (C=O); 140.5, 140.4, 128.1, 127.8, 126.2
(Carom); 48.9 (C5, C6); 48.3 (C2, C3); 39.8 (C1, C4);
29.3 (C7). Found, %: C 65.68; H 4.73; N 10.89.
C14H12N2O3. Calculated, %: C 65.63; H 4.69; N 10.94.
exo-5,6-Epoxy-N-(3-pyridyl)bicyclo[2.2.1]hept-
ane-endo-2,endo-3-dicarboximide (VIb). Yield 0.32 g
(63%), mp 226.5–228°C. IR spectrum, Ȟ, cm–1: 3030,
1
1780, 1710, 1595, 1500, 1445, 1180, 860. H NMR
spectrum, į, ppm: 8.59, 8.35, 7.77, 7.56 (4H, Harom);
3.43 m (2H, 5-H, 6-H); 3.38 m (2H, 2-H, 3-H); 2.97 m
(2H, 1-H, 4-H); 1.42 d (1H, syn-7-H); 1.14 d (1H, anti-
b. The reaction was carried out as described above
in a with the same amounts of the reactants. When the
reaction was complete, the mixture was neutralized
with a saturated solution of sodium carbonate, the
organic phase was separated, and the aqueous phase
was washed with three portions of ethyl acetate. The
extracts were combined with the organic phase, the
2
7-H, J7,7 = 9.4 Hz). Found, %: C 65.70; H 4.71;
N 10.85. C14H12N2O3. Calculated, %: C 65.63; H 4.69;
N 10.94.
exo-5,6-Epoxy-N-(3-hydroxy-2-pyridyl)bicyclo-
[2.2.1]heptane-endo-2,endo-3-dicarboximide (VId).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

KAS’YAN et al.
1538
4. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
solvent was removed under reduced pressure, and the
residue was recrystallized from 2-propanol. We thus
isolated 0.24 g (40%) of exo-2-hydroxy-endo-9-(2-
pyridylcarbamoyl)-4-oxatricyclo[4.2.1.03,7]nonan-5-
one (VII), mp 116–118°C. IR spectrum, Ȟ, cm–1: 3440,
Moscow: Novaya Volna, 2002, 14th ed.
5. Kas’yan, L.I., Krishchik, O.V., Pal’chikov, V.A., and
Tarabara, I.N., Vɿsn. Dnɿpropetr. Univ. Khɿm., 2004,
no. 10, p. 10; Kas’yan, L.I., Krishchik, O.V., Krasov-
skii, V.A., Okovityi, S.I., Tarabara, I.N., and Pal’chi-
kov, V.A., Vopr. Khim. Khim. Tekhnol., 2004, no. 2,
p. 35; Kas’yan, A.O., Tarabara, I.N., Zlenko, E.T., Oko-
vityi, S.I., and Kas’yan, L.I., Russ. J. Org. Chem., 1999,
vol. 35, p. 1018; Kas’yan, A.O., Krishchik, O.V., Kras-
novskaya, O.Yu., and Kas’yan, L.I., Russ. J. Org.
Chem., 1998, vol. 34, 1731; Kas’yan, L.I., Kri-
shchik, O.V., Tarabara, I.N., and Kas’yan, A.O., Vopr.
Khim. Khim. Tekhnol., 2001, no. 5, p. 35.
6. Gol’dfarb, Ya.L., Belen’kii, L.I., Abronin, I.A., Zhido-
mirov, G.M., and Chuvylkin, N.D., Zh. Obshch. Khim.,
1973, vol. 43, p. 2730.
7. Jonson, A.W., King, T.J., and Turner, J.R., J. Chem.
Soc., 1960, p. 1509; Dorn, H. and Hilgetag, G., Chem.
Ber., 1964, vol. 97, p. 695.
1
1779, 1689, 1530, 1256, 1193, 1157, 1015. H NMR
spectrum, į, ppm: 10.69 s (1H, NH); 8.36, 8.21, 7.39,
7.14 (4H, Harom); 5.15 (1H, OH); 4.35 d (1H, 3-H,
3J3,7 = 4.4 Hz); 4.24 s (1H, 2-H); 3.60 m (1H, 6-H,
3J6,9 = 10.9 Hz); 3.30 m (1H, 7-H); 2.78 m (1H, 9-H,
3J9,1 = 4.1 Hz); 2.47 br.s (1H, 1-H); 2.01 d (1H, syn-
2
8-H); 1.47 d (1H, anti-8-H, J8,8 = 10.5 Hz). Found, %:
C 61.35; H 5.14; N 10.27. C14H14N2O4. Calculated, %:
C 61.31; H 5.11; N 10.22.
Oxidation of endo-3-(2-pyridylcarbamoyl)bi-
cyclo[2.2.1]hept-5-ene-endo-2-carboxylic acid (IVa).
Amido acid IVa, 0.52 g (2 mmol), was dissolved in
5 ml of 98% formic acid, the solution was cooled to
0°C, 0.23 ml (4 mmol) of 50% hydrogen peroxide was
added under stirring, and the mixture was stirred until
the reaction was complete (TLC). Formic acid was
removed under reduced pressure to leave an oily sub-
8. Kolotova, N.V., Dolzhenko, A.V., Koz’minykh, V.O.,
Kotegov, V.P., and Godina, A.T., Khim.-Farm. Zh.,
1999, vol. 33, p. 9.
9. Nakanishi, K., Infrared Absorption Spectroscopy. Prac-
tical, San Francisco: Holden-Day, 1962; Bellamy, L.J.,
The Infra-red Spectra of Complex Molecules, London:
Methuen, 1958.
1
stance (82%) which, according to the H NMR data,
was a mixture of compound VII (29%) and 2-pyri-
dylammonium exo-2-hydroxy-5-oxo-4-oxatricyclo-
[4.2.1.03,7]nonane-endo-9-carboxylate (IX) (71%). IR
spectrum, Ȟ, cm–1: 3360, 3010, 2740, 1785, 1690,
10. Zefirov, N.S. and Sokolov, V.I., Usp. Khim., 1967,
vol. 36, p. 243.
1
11. Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, p. 209.
12. Ruud, K., Helgaker, T., Bak, K.L., Jorgensen, P., and
Jensen, H.J.A., J. Chem. Phys., 1993, vol. 99, p. 3847.
1590, 1560, 1240, 1220, 1175, 1030. H NMR spec-
trum, į, ppm: VII: 10.64 s (1H, NH); 8.30, 8.22, 7.38,
7.12 (4H, Harom); 5.24 (1H, OH); 4.35 d (1H, 3-H,
3J3,7 = 4.8 Hz); 4.29 s (1H, 2-H); 3.62 m (1H, 6-H,
3J6,9 = 10.8 Hz); 3.25 m (1H, 7-H), 2.75 m (1H, 9-H,
3J9,1 = 4.5 Hz); 2.48 br.s (1H, 1-H); 2.02 d (1H, syn-
13. Kas’yan, L.I., Krishchik, O.V., and Tarabara, I.N., Vɿsn.
Dnɿpropetr. Univ. Khɿm., 2002, no. 7, p. 42; Kas’-
yan, L.I., Krishchik, O.V., Umrykhina, L.K., and Kas’-
yan, A.O., Vɿsn. Dnɿpropetr. Univ. Khɿm., 1998, no. 3,
p. 87; Kas’yan, L.I., Seferova, M.F., and Okovityi, S.I.,
Alitsiklicheskie epoksidnye soedineniya. Metody sinteza
(Alicyclic Epoxy Compounds. Methods of Synthesis),
Dnepropetrovsk: Dnepropetr. Gos. Univ., 1996.
2
8-H); 1.46 d (1H, anti-8-H, J8,8 = 11.4 Hz); IX: 8.16
(3H, H3N+); 8.00, 7.88, 7.77, 7.38 (4H, Harom); 5.52
3
(1H, OH); 4.32 d (1H, 3-H, J3,7 = 5.1 Hz); 4.02 s
(1H, 2-H); 3.20 m (1H, 7-H); 3.04 m (1H, 6-H, 3J6,9
10.7 Hz); 2.67 m (1H, 9-H, J9,1 = 4.7 Hz); 2.42 br.s
(1H, 1-H); 1.95 d (1H, syn-8-H); 1.51 d (1H, anti-8-H,
2J8,8 = 11.0 Hz).
=
3
14. Prilezhaeva, E.N., Reaktsiya Prilezhaeva. Elektrofil’noe
okislenie (Prilezhaev Reaction. Electrophilic Oxidation),
Moscow: Nauka, 1974.
15. Kas’yan, L.I., Usp. Khim., 1998, vol. 67, p. 299.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005