Synthesis and some chemical transformations of adamantyl-substituted pyrazolones

Article abstract of DOI:10.1134/S1070428010100209

1-Substituted 3-(1-adamantyl)-4,5-dihydro-1H-pyrazol-5-ones and 3-(1-adamantyl)-4,5-dihydroiso-xazol-5-one were synthesized by reaction of ethyl 3-(1-adamantyl)-3-oxopropanoate with various hydrazine derivatives and hydroxylamine hydrochloride. Nitrosatio

Full text of DOI:10.1134/S1070428010100209

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 10, pp. 1558–1562. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © K.M. Bormasheva, S.A. Kon’kov, I.K. Moiseev, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 10,
pp. 1552–1555.
Synthesis and Some Chemical Transformations
of Adamantyl-Substituted Pyrazolones
K. M. Bormasheva, S. A. Kon’kov, and I. K. Moiseev
Samara State Technical University, ul. Molodogvardeiskaya 244, Samara, 443100 Russia
e-mail: ikmoiseev@mail.ru
Received January 25, 2010
Abstract—1-Substituted 3-(1-adamantyl)-4,5-dihydro-1H-pyrazol-5-ones and 3-(1-adamantyl)-4,5-dihydroiso-
xazol-5-one were synthesized by reaction of ethyl 3-(1-adamantyl)-3-oxopropanoate with various hydrazine
derivatives and hydroxylamine hydrochloride. Nitrosation of adamantyl-substituted pyrazolones with sodium
nitrite in acetic acid gave the corresponding 4-hydroxyimino derivatives. Reactions of 3-(1-adamantyl)-4,5-di-
hydro-1H-pyrazol-5-ones and 3-(1-adamantyl)-4,5-dihydroisoxazol-5-one with aromatic and heterocyclic alde-
hydes led to the formation of condensation products at position 4 of the heteroring.
DOI: 10.1134/S1070428010100209
1,2-Diazole derivatives are used as pyrazolone
dyes, materials for optoelectronics, pesticides, and
medical agents, and they attract interest due to diver-
sity of their chemical transformations. Many drugs
(e.g., aminophenazone, metamizole sodium, celecoxib,
phenazone) are heterocyclic derivatives of 1,3-dicar-
bonyl compounds [1].
3-(1-adamantylmethyl)-4,5-dihydro-1H-pyrazol-5-one
or 3-(1-adamantylmethyl)-1-phenyl-4,5-dihydro-1H-
pyrazol-3-one [from ethyl 4-(1-adamantyl)-2-acetyl-3-
oxobutanoate] or decomposition of the initial dioxo
ester with formation of adamantane-1-carbohydrazide
[from ethyl 2-(1-adamantylcarbonyl)-3-oxobutanoate.
Due to the presence of an activated methylene
group in position 4, 3-methyl-1-phenyl-4,5-dihydro-
1H-pyrazol-5-one undergoes halogenation, nitrosation,
nitration, and condensation with benzaldehyde and
acetone [5]. There are no published data on the chem-
ical behavior of adamantyl-substituted pyrazolones. In
the present article we report the results of our study on
the synthesis of adamantyl-substituted pyrazolones and
their chemical transformations. Pyrazolones IIa–IId
3-(1-Adamantyl)- and 3-(1-adamantylmethyl)-1-
phenyl-4,5-dihydro-1H-pyrazol-5-ones were synthe-
sized for the first time from keto esters [2, 3], and their
chemical behavior was not studied. Reactions of ada-
mantyl-containing dioxocarboxylic acid esters with
hydrazine and phenylhydrazine were reported [4];
depending on the initial ester, the reaction involved
either elimination of acetyl group with formation of
Scheme 1.
O
O
O
O
RNHNH2
N
N
HN
N
R
R
A
A
IIa–IId
B
OEt
O
O
NH2OH·HCl
I
N
O
N
O
III
B
R = H (a), Ph (b), CONH2 (c), 4-O2NC6H4 (d).
1558

SYNTHESIS AND SOME CHEMICAL TRANSFORMATIONS OF ADAMANTYL-...
1559
Scheme 2.
OH
NO
N
NaNO2, AcOH
O
O
IIa–IIc
N
N
N
N
R
R
IVa–IVc
R = H (a), Ph (b), CONH2 (c).
droxyimino derivatives IVa–IVc (Scheme 2). Reac-
tions of compounds IIa, IIb, IId, and III with aromat-
ic and heterocyclic aldehydes gave condensation prod-
ucts V–IX (Schemes 3, 4).
and isoxazolone III were synthesized by reactions of
ethyl 3-(1-adamantyl)-3-oxopropanoate (I) with substi-
tuted hydrazines and hydroxylamine hydrochloride,
respectively (Scheme 1).
It is known that pyrazol-5-one derivatives can exist
as three tautomers [6]. The H NMR spectra of com-
EXPERIMENTAL
1
pounds IIa, IIb, IId, and III in DMSO-d6 contained
a singlet at δ 4.90–5.48 ppm (1H) due to proton in
position 4 of the heteroring and a broadened singlet at
δ 10.20–12.05 ppm (1H) due to NH proton. In the
spectra of the same compounds in CDCl3 we observed
a two-proton singlet in the region 3.33–4.65 ppm
(C4H2). These findings led us to conclude that com-
pounds IIa, IIb, IId, and III in nonpolar solvent
(CDCl3) exist mainly as tautomers A and that structure
B predominates in polar solvent (DMSO-d6). We failed
The IR spectra were measured in KBr on
a Shimadzu FTIR-8400S instrument. The H NMR
1
spectra were recorded on a Bruker AM-300 spectrom-
eter at 300 MHz using tetramethylsilane as internal
reference. The elemental compositions were deter-
mined on a Euro Vector EA3000 CHNSO analyzer.
The purity of the products was checked by TLC on
Silufol UV-254 plates (development with iodine vapor)
and GLC (Kristall 2000-M).
1
to obtain the H NMR spectrum of pyrazole IIc in
CDCl3 due to its poor solubility. Our results are con-
sistent with published data [7].
3-(1-Adamantyl)-4,5-dihydro-1H-pyrazol-5-one
(IIa) was synthesized according to the procedure de-
scribed in [4]. Colorless crystals, mp 294–296°C; pub-
lished data [4]: mp 292.5–295.5°C.
By nitrosation of pyrazolones IIa–IIc with sodium
nitrite in acetic acid we obtained the corresponding hy-
3-(1-Adamantyl)-1-phenyl-4,5-dihydro-1H-pyra-
zol-5-one (IIb) was synthesized according to the
procedure described in [2]. Yellow crystals, mp 140–
141.5°C; published data [2]: mp 138–139°C.
Scheme 3.
R'
3-(1-Adamantyl)-5-oxo-2,5-dihydro-1H-pyrazole-
1-carboxamide (IIc). A mixture of 1.78 g (16 mmol)
of semicarbazide hydrochloride and 1.69 g (16 mmol)
of sodium carbonate in 7 ml of water was added to
a solution of 2 g (8 mmol) of ester I in 15 ml of
ethanol. The mixture was heated for 2 h under reflux
with stirring, and the precipitate was filtered off and
recrystallized from ethanol. Yield 1.53 g (73%), color-
less crystals, mp 302–304°C. IR spectrum, ν, cm–1:
3398, 3209 (NH2); 2905, 2851 (C–HAd); 1686 (C5=O);
R'CHO
O
IIa, IIb, IId
N
N
R
Va, Vb, Vd, VIb, VIIa
VIIb, VIId, VIIIb
R = H (a), Ph (b), 4-O2NC6H4 (d); V, R′ = Ph; VI, R′ =
4-MeOC6H4; VII, R′ = 2-furyl; VIII, R′ = 2-thienyl.
Scheme 4.
R
1
1601 (1-C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 1.90–2.13 m (15H, Ad), 5.20 s (1H, CH), 5.81 s
(3H, NH). Found, %: C 64.25; H 7.12; N 16.08.
C14H19N3O2. Calculated, %: C 64.37; H 7.28; N 16.09.
RCHO
O
III
N
O
IXa–IXc
Compounds IId and III were synthesized in a sim-
R = Ph (a), 4-MeOC6H4 (b), 2-furyl (c).
ilar way.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

BORMASHEVA et al.
1560
3-(1-Adamantyl)-1-(4-nitrophenyl)-4,5-dihydro-
(DMSO-d6), δ, ppm: 1.66 m (6H, Ad), 1.98 m (9H,
Ad), 7.13 t (1H, p-H, J = 6.54 Hz), 7.36 t (2H, m-H,
J = 6.54 Hz), 7.77 d (2H, o-H, J = 6.54 Hz), 14.53 s
(1H, NOH). Found, %: C 70.32; H 6.44; N 12.89.
C19H21N3O2. Calculated, %: C 70.59; H 6.50; N 13.00.
1H-pyrazol-5-one (IId) was synthesized from 2.5 g
(10 mmol) of compound I and 1.7 g (11 mmol) of
4-nitrophenylhydrazine. Yield 2.16 g (64%), orange
crystals, mp 230–232°C (from ethanol). IR spectrum,
ν, cm–1: 3550–3200 (N–H); 3113 (C–Harom); 2912,
2851 (C–HAd); 1724 (C=O); 1593 (C=C, C=N); 1512
(NO2, asym.); 1323 (NO2, sym). 1H NMR spectrum, δ,
ppm: in DMSO-d6: 1.50 s (6H, Ad), 1.76 s (6H, Ad),
2.04 s (3H, Ad), 5.48 s (1H, CH), 8.07 d (2H, o-H,
J = 9.3 Hz), 8.30 d (2H, m-H, J = 9.3 Hz), 12.05 br.s
(1H, NH); in CDCl3: 1.75 m (12H, Ad), 2.05 s (3H,
Ad), 3.42 s (2H, CH2), 8.08 d (2H, o-H, J = 9.3 Hz),
8.18 d (2H, m-H, J = 9.0 Hz). Found, %: C 67.50;
H 6.21; N 12.45. C19H21N3O3. Calculated, %: C 67.26;
H 6.19; N 12.39.
3-(1-Adamantyl)-4-hydroxyimino-5-oxo-4,5-di-
hydro-1H-pyrazole-1-carboxamide (IVc) was syn-
thesized from 0.6 g (2.3 mmol) of compound IIc in
10 ml of acetic acid and 0.3 g (4.6 mmol) of sodium
nitrite. Yield 0.40 g (60%), yellow crystals, mp 260–
263°C. IR spectrum, ν, cm–1: 3333 (O–H); 3186
(N–H); 2905, 2851 (C–HAd); 1728 (C5=O); 1620
1
(1-C=O); 1502, 1461 (C=C, C=N). H NMR spectrum
(DMSO-d6), δ, ppm: 1.71–2.03 m (15H, Ad), 7.89 s
(3H, OH, NH2). Found, %: C 57.67; H 6.12; N 19.24.
C14H18N4O3. Calculated, %: C 57.93; H 6.21; N 19.31.
3-(1-Adamantyl)-4,5-dihydroisoxazol-5-one (III)
was synthesized from 2 g (8 mmol) of compound I and
0.56 g (8 mmol) of hydroxylamine hydrochloride.
Yield 0.55 g (49%), colorless crystals, mp 160–161°C
(from ethanol). IR spectrum, ν, cm–1: 2908, 2851
3-(1-Adamantyl)-4-benzylidene-4,5-dihydro-1H-
pyrazol-5-one (Va). A mixture of 0.6 g (2.8 mmol) of
compound IIa and 5 ml (5.25 g, 49.5 mmol) of benz-
aldehyde was heated for 2 h under reflux. The precip-
itate was filtered off and washed with propan-2-ol.
Yield 0.82 g (98%), colorless crystals, mp >340°C. IR
spectrum, ν, cm–1: 3120–2000 (N–H); 3080 (C–Harom);
2905, 2851 (C–HAd); 1705 (C=O); 1578, 1531, 1492
1
(C–HAd); 1801 (C=O). H NMR spectrum, δ, ppm: in
DMSO-d6: 1.57–2.00 m (15H, Ad), 4.95 (1H, CH),
9.25 br.s (1H, NH); in CDCl3: 1.64–2.03 m (15H, Ad),
3.33 (2H, CH2). Found, %: C 71.10; H 7.54; N 6.32.
C13H17NO2. Calculated, %: C 71.23; H 7.76; N 6.39.
1
(C=C, C=N). H NMR spectrum (CDCl3), δ, ppm:
1.60–1.68 m (6H, Ad), 1.91–2.09 m (9H, Ad), 7.15–
7.38 m (6H, CH, Ph), 14.84 br.s (1H, NH). Found, %:
C 78.56; H 7.23; N 9.21. C20H22N2O. Calculated, %:
C 78.43; H 7.19; N 9.15.
3-(1-Adamantyl)-4-hydroxyimino-4,5-dihydro-
1H-pyrazol-5-one (IVa). Compound IIa, 1.1 g
(5 mmol), was dissolved in 10 ml of glacial acetic acid,
and 0.69 g (10 mmol) of sodium nitrite was added. The
original dark orange solution turned yellow in 1 h. It
was stirred for an additional 2 h and poured into water,
and the precipitate was filtered off and recrystallized
from ethanol. Yield 1.25 g (96%), yellow crystals,
mp 248–250°C. IR spectrum, ν, cm–1: 3600–2400 (OH,
NH); 2905, 2851 (C–HAd); 1697 (C=O); 1616 (C=N).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.62–1.70 m
(6H, Ad), 1.88–2.00 m (9H, Ad), 11.31 br.s (1H, NH),
13.39 (1H, OH). Found, %: C 63.32; H 6.90; N 17.07.
C13H17N3O2. Calculated, %: C 63.16; H 6.88; N 17.00.
Compounds Vb, Vd, VIb, VIIa, VIIb, VIId, VIIIb,
and IXa–IXc were synthesized in a similar way.
3-(1-Adamantyl)-4-benzylidene-1-phenyl-4,5-di-
hydro-1H-pyrazol-5-one (Vb) was synthesized from
2.35 g (8 mmol) of compound IIb and 10 ml (10.5 g,
99 mmol) of benzaldehyde. Yield 3.03 g (96%), red
crystals, mp 213–214°C (from ethanol). IR spectrum,
ν, cm–1: 3067 (C–Harom); 2928, 2905, 2851 (C–HAd);
1
1686 (C=O); 1597, 1497 (C=C, C=N). H NMR spec-
trum (DMSO-d6), δ, ppm: 1.81 q (6H, Ad, J =
13.6 Hz), 2.11 d (9H, Ad, J = 11.7 Hz), 7.18 t (1H,
p-H, J = 6.4 Hz), 7.43 t (2H, m-H, J = 6.4 Hz), 7.50–
7.60 m (3H, m′-H, p′-H, Ph), 7.90 d (2H, o′-H, J =
6.4 Hz), 8.18 s (1H, =CHPh), 8.40 d (2H, o-H, J =
7.0 Hz). Found, %: C 81.78; H 6.88; N 7.09.
C26H26N2O. Calculated, %: C 81.68; H 6.81; N 7.33.
Compounds IVb and IVc were synthesized in
a similar way.
3-(1-Adamantyl)-4-hydroxyimino-1-phenyl-4,5-
dihydro-1H-pyrazol-5-one (IVb) was synthesized
from 7.35 g (25 mmol) of compound IIb in 60 ml of
acetic acid and 3.15 g (45 mmol) of sodium nitrite.
Yield 7.97 g (100%), yellow crystals, mp 210–212°C.
IR spectrum, ν, cm–1: 3510–3300 (O–H); 3080
(C–Harom); 2912, 2851 (C–HAd); 1672 (C=O); 1589,
3-(1-Adamantyl)-4-benzylidene-1-(4-nitrophen-
yl)-4,5-dihydro-1H-pyrazol-5-one (Vd) was synthe-
sized from 0.7 g (2.06 mmol) of compound IId and
5 ml (5.25 g, 49.5 mmol) of benzaldehyde. Yield
0.81 g (92%), brown crystals, mp 247–248°C (from
1
1502, 1495 (C=C, C=N). H NMR spectrum
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

SYNTHESIS AND SOME CHEMICAL TRANSFORMATIONS OF ADAMANTYL-...
1561
ethanol). IR spectrum, ν, cm–1: 3072 (C–Harom); 2901,
green crystals, mp 262–264°C (from ethanol). IR spec-
trum, ν, cm–1: 3132 (C–HFu); 2908, 2847 (C–HAd);
1697 (C=O); 1593, 1523, 1497 (C=C, C=N); 1512
2854 (C–HAd); 1695 (C=O); 1591, 1497 (C=C, C=N);
1
1510 (NO2, asym.); 1336 (NO2, sym.). H NMR spec-
1
trum (CDCl3), δ, ppm: 1.74–2.12 m (15H, Ad), 7.38–
7.60 m (5H, Ph), 7.99 s (1H, CH), 8.04–8.19 m
(4H, C6H4). Found, %: C 73.12; H 5.89; N 9.76.
C26H25N3O3. Calculated, %: C 73.07; H 5.85; N 9.84.
(NO2, asym.); 1319 (NO2, sym.). H NMR spectrum
(CDCl3), δ, ppm: 1.80 s (6H, Ad), 2.10 s (9H, Ad),
6.71 s (1H, 3′-H), 7.74 s (1H, 4′-H), 7.83 s (1H, 5′-H),
8.23 s (4H, C6H4), 8.70 s (1H, CH). Found, %:
C 69.12; H 5.59; N 10.23. C24H23N3O4. Calculated, %:
C 69.06; H 5.52; N 10.07.
3-(1-Adamantyl)-4-(4-methoxybenzylidene)-
1-phenyl-4,5-dihydro-1H-pyrazol-5-one (VIb) was
synthesized from 0.6 g (2 mmol) of compound IIb and
5 ml (5.6 g, 41.4 mmol) of 4-methoxybenzaldehyde.
Yield 0.7 g (83%), orange crystals, mp 180–182°C
(from ethanol). IR spectrum, ν, cm–1: 3070 (C–Harom);
2901, 2885, 2846 (C–HAd); 1686 (C=O); 1578, 1531,
3-(1-Adamantyl)-1-phenyl-4-[(2-thienyl)methyli-
dene]-4,5-dihydro-1H-pyrazol-5-one (VIIIb) was
synthesized from 0.6 g (2 mmol) of compound IIb and
0.46 g (4 mmol) of thiophene-2-carbaldehyde. Yield
0.63 g (80%), red crystals, mp 229–231°C (from
ethanol). IR spectrum, ν, cm–1: 3060 (C–Harom); 2901,
2847 (C–HAd); 1670 (C=O); 1593 (C=Carom); 1535,
1
1497 (C=C, C=N). H NMR spectrum (DMSO-d6), δ,
ppm: 1.70–1.85 m (7H, Ad), 2.05–2.10 m (8H, Ad),
3.86 s (3H, CH3), 7.06–7.08 m (2H, o′-H), 7.15–
7.16 m (1H, p-H), 7.38–7.42 m and 7.88–7.90 m (2H
each, m-H, m′-H), 8.05 s (1H, =CH), 8.61 d (2H, o-H,
J = 9.2 Hz). Found, %: C 78.70; H 6.84; N 6.89.
C27H28N2O2. Calculated, %: C 78.64; H 6.80; N 6.80.
1
1497 (C=C, C=N). H NMR spectrum (CDCl3), δ,
ppm: 1.86 s (6H, Ad), 2.18 s (9H, Ad), 7.15–7.27 m
(2H, 3′-H, p-H), 7.42 t (2H, m-H, J = 9.0 Hz), 7.85–
7.90 m (2H, 4′-H, 5′-H), 8.07 d (2H, o-H, J = 9.0 Hz),
8.16 d (1H, =CH). Found, %: C 74.25; H 6.17; N 7.29.
C19H21N3O3. Calculated, %: C 74.23; H 6.19; N 7.22.
3-(1-Adamantyl)-4-furfurylidene-4,5-dihydro-
1H-pyrazol-5-one (VIIa) was synthesized from 0.6 g
(2.8 mmol) of compound IIa and 0.54 g (5.6 mmol) of
furfurol. Yield 0.62 g (77%), yellow crystals, mp 197–
200°C. IR spectrum, ν, cm–1: 3117 (C–HFu); 3300–
2090 (N–H); 2905, 2851 (C–HAd); 1690 (C=O); 1636,
3-(1-Adamantyl)-4-benzylidene-4,5-dihydroiso-
xazol-5-one (IXa) was synthesized from 0.5 g
(2.3 mmol) of compound III and 5 ml (5.25 g,
49.5 mmol) of benzaldehyde. Yield 0.65 g (93%),
colorless crystals, mp 218–221°C (from ethanol). IR
spectrum, ν, cm–1: 3065 (C–Harom); 2889, 2851
(C–HAd); 1747 (C=O); 1608, 1566, 1539 (C=C, C=N).
1H NMR spectrum (CDCl3), δ, ppm: 1.84–2.18 m
(15H, Ad), 7.50–8.23 m (5H, Ph), 8.01 s (1H, CH).
Found, %: C 78.09; H 6.89; N 4.56. C20H21NO2. Cal-
culated, %: C 78.18; H 6.84; N 4.56.
1
1601, 1574, 1539 (C=C, C=N). H NMR spectrum
(DMSO-d6), δ, ppm: 1.66–2.01 m (15H, Ad), 6.66–
6.67 m (1H, 3′-H), 7.07–7.08 m (1H, 4′-H), 7.90 m
(1H, 5′-H), 8.47 s (1H, CH), 11.42 br.s (1H, NH).
Found, %: C 72.89; H 6.70; N 9.40. C18H20N2O2. Cal-
culated, %: C 72.97; H 6.76; N 9.46.
3-(1-Adamantyl)-4-furfurylidene-1-phenyl-4,5-
dihydro-1H-pyrazol-5-one (VIIb) was synthesized
from 0.6 g (2 mmol) of compound IIb and 0.38 g
(4 mmol) of furfurol. Yield 0.64 g (84%), red crystals,
mp 218–220°C (from ethanol). IR spectrum, ν, cm–1:
3140, 3080 (C–HFu); 2928, 2901, 2851 (C–HAd); 1682
(C=O); 1597, 1520, 1497 (C=C, C=N). 1H NMR spec-
trum (CDCl3), δ, ppm: 1.65 s (6H, Ad), 2.17 s (9H,
Ad), 6.72–6.73 m (1H, 3′-H), 7.18 t (1H, p-H, J =
6.0 Hz), 7.42 t (2H, m-H, J = 9.0 Hz), 7.75 s (1H,
4′-H), 7.84 s (1H, 5′-H), 8.03 d (2H, o-H, J = 9.0 Hz),
8.78–8.79 d (1H, =CH, J = 3.0 Hz). Found, %:
C 77.34; H 6.40; N 7.51. C24H24N2O2. Calculated, %:
C 77.42; H 6.45; N 7.53.
3-(1-Adamantyl)-4-(4-methoxybenzylidene)-4,5-
dihydroisoxazol-5-one (IXb) was synthesized from
0.5 g (2.3 mmol) of compound III and 5 ml (5.6 g,
41.4 mmol) of 4-methoxybenzaldehyde. Yield 0.58 g
(75%), orange crystals, mp 177–180°C (from ethanol).
IR spectrum, ν, cm–1: 3065 (C–Harom); 2901, 2851
(C–HAd); 1732 (C=O); 1574, 1531 (C=C, C=N); 1273
1
(C–O). H NMR spectrum (CDCl3), δ, ppm: 1.77–
2.07 m (15H, Ad), 3.86 s (3H, CH3), 6.94 d (2H, o-H,
J = 8.7 Hz), 7.86 s (1H, =CH), 8.29 d (2H, m-H,
J = 8.4 Hz). Found, %: C 74.98; H 6.84; N 4.23.
C21H23NO3. Calculated, %: C 74.78; H 6.82; N 4.15.
3-(1-Adamantyl)-4-furfurylidene-4,5-dihydroiso-
xazol-5-one (IXc) was synthesized from 0.5 g
(2.3 mmol) of compound III and 0.38 g (4 mmol) of
furfural. Yield 0.58 g (85%), brown crystals, mp 200–
204°C (from ethanol). IR spectrum, ν, cm–1: 3109,
3-(1-Adamantyl)-4-furfurylidene-1-(4-nitro-
phenyl)-4,5-dihydro-1H-pyrazol-5-one (VIId) was
synthesized from 0.5 g (1.5 mmol) of compound IId
and 0.54 g (5.6 mmol) of furfural. Yield 0.55 g (89%),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010

BORMASHEVA et al.
1562
3. Stepanov, F.N., Sidorova, L.I., and Dovgan’, N.A.,
Zh. Org. Khim., 1972, vol. 8, p. 1834.
4. Bormasheva, K.M., Nechaeva, O.V., and Moiseev, I.K.,
Russ. J. Org. Chem., 2008, vol. 44, p. 1760.
5. Knorre, L., Justus Liebigs Ann. Chem., 1887, vol. 238,
3080 (C–HFu); 2928, 2905, 2854 (C–HAd); 1747 (C=O);
1604, 1527, 1450 (C=C, C=N). H NMR spectrum
(CDCl3), δ, ppm: 1.77–2.08 m (15H, Ad), 6.69–6.70 m
(1H, 3′-H), 7.73 s (1H, 4′-H), 7.79 s (1H, =CH), 8.56–
8.57 m (1H, 5′-H). Found, %: C 72.87; H 6.54; N 4.82.
C18H19NO3. Calculated, %: C 72.73; H 6.40; N 4.71.
1
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010