New synthesis of 3-amino-1H-benzo[f]chromene-2-carbonitriles

Article abstract of DOI:10.1134/S1070428013030147

3-Amino-1H-benzo[f]chromene-2-carbonitriles were synthesized by non-catalytic reaction from Mannich bases of the naphthalene series and malononitrile. Reactive 1-benzylidene(or methylidene)naphthalen-2(1H)-ones were presumed as intermediate products.

Full text of DOI:10.1134/S1070428013030147

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 3, pp. 398–402. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © D.V. Osipov, V.A. Osyanin, Yu.N. Klimochkin, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 3,
pp. 412–415.
Dedicated to Full Member of the Russian Academy of Sciences
I.P. Beletskaya on her jubilee
New Synthesis of 3-Amino-1H-benzo[f]chromene-2-carbonitriles
D. V. Osipov, V. A. Osyanin, and Yu. N. Klimochkin
Samara State Technical University, ul. Molodogvardeiskaya 244, Samara, 443100 Russia
e-mail: VOsyanin@mail.ru
Received December 26, 2012
Abstract—3-Amino-1H-benzo[f]chromene-2-carbonitriles were synthesized by non-catalytic reaction from
Mannich bases of the naphthalene series and malononitrile. Reactive 1-benzylidene(or methylidene)naphthalen-
2(1H)-ones were presumed as intermediate products.
DOI: 10.1134/S1070428013030147
Studies on the synthesis of fused aminochromenes
are stimulated by diverse biological activity of these
compounds. In particular, they exhibit antioxidant
properties [1], while substituted 2-amino-4H-benzo-
chromenes were proposed as medicines for the treat-
ment of immune disorders and diabetes complications
[2]. Some 3-amino-1H-benzo[f]chromene-2-carboni-
triles were reported to possess anticancer [3] and anti-
bacterial [4] activity. Furthermore, 3-amino-1H-benzo-
[f]chromene-2-carbonitriles may be regarded as hetero-
cyclic β-enamino nitriles that are promising as building
blocks for the synthesis of fused chromenes.
nitrile, and the Hantzsch ester in the presence of InCl3
[19]. Enantioselective synthesis of 3-amino-1H-benzo-
[f]chromene-2-carbonitriles from benzylidenemalono-
nitriles was also reported [20].
We now propose a new procedure for the synthesis
of 1-substituted 3-amino-1H-benzo[f]chromene-2-car-
bonitriles IIa–IIj from Mannich bases Ia–Ij of the
naphthalene series and malononitrile. The reactions
were carried out by heating equimolar amounts of the
reactants in ethanol for 1 h, and compounds IIa–IIj
were isolated in 72–90% yield. The nature of the R
substituent does not affect the yield to a considerable
extent. Apart from high yield and experimental sim-
plicity, the proposed procedure is advantageous since
there is no need of using additional catalyst. Moreover,
the use of Mannich bases as starting compounds makes
it possible to avoid side formation of 14H-dibenzo[a,j]-
xanthenes, which frequently accompanies three-com-
ponent condensations with naphthalen-2-ol [3, 21, 22].
Several procedures for the synthesis of 3-amino-
1H-benzo[f]chromene-2-carbonitriles have been re-
ported. Among these, the most commonly used is
three-component condensation of malononitrile with
an aldehyde, primarily aromatic one, and naphthalen-
2-ol. This reaction is generally carried out in ethanol,
acetonitrile, or water in the presence of a base (K2CO3
[4], NaHCO3 [5], triethylamine [6], DABCO [7]), acid
(TiCl4 [8], H14[NaP5W30O110] [9]), or phase-transfer
catalyst (cetyltrimethylammonium bromide [10] or
chloride [11, 12], tetrabutylammonium bromide [13],
sodium dodecanesulfonate [14]), as well as of ceric
ammonium nitrate [3]. Another procedure includes
preliminary preparation of alkylidenemalononitrile and
its subsequent reaction with naphthalen-2-ol in the
presence of piperidine [15–17] or sodium hydroxide
[18] as base. 3-Amino-1H-benzo[f]chromene-2-carbo-
nitrile having no substituent on C1 was synthesized
from 2-hydroxynaphthalene-1-carbaldehyde, malono-
The described reaction is a cascade process which
is likely to include deamination of Mannich base with
formation of intermediate o-quinone methide A,
Michael addition of malononitrile, and intramolecular
Pinner reaction [23] between the hydroxy and cyano
groups. The subsequent proton migration yields final
product II. Presumably, dimethylamine liberated in the
first step favors deprotonation of malononitrile. We
detected no 9,11-diamino-12H-benzo[5,6]chromeno-
[2,3-b]pyridine-10-carbonitriles [24] that could be
formed via addition of the second malononitrile mole-
cule to benzochromenes II.
398

NEW SYNTHESIS OF 3-AMINO-1H-BENZO[f]CHROMENE-2-CARBONITRILES
399
Scheme 1.
R
NMe2
OH
R
O
EtOH
+
CH2(CN)2
+
CH(CN)2
–Me2NH2
R'
R'
Ia–Ij
A
CN
CN
CN
R
R
NH
R
NH2
CN
O
~H+
Me2NH2
–Me2NH
O
O
R'
R'
R'
IIa–IIj
R′ = H, R = H (a), Ph (b), 4-MeOC6H4 (c), 3-O2NC6H4 (d), 2-FC6H4 (e), pyridin-4-yl (f), thiophen-2-yl (g),
1-benzyl-1H-imidazol-5-yl (h), 4-ClC6H4 (i); R′ = adamantan-1-yl, R = H (j).
On the whole, quinone methides of the naphtha-
lene series can be generated under considerably milder
conditions than quinone methides of the benzene
series, primarily due to extended conjugation chain in
the former. Mannich base Ih is converted into the
corresponding o-quinone methides even at room tem-
perature, as follows from the appearance of bright
orange color upon dissolution of the colorless pre-
cursor in ethanol. Benzochromene IIh is formed in
75% yield from compound Ih and malononitrile in
48 h, whereas Mannich bases of the phenol series fail
to react with malononitrile even on prolonged heating
in boiling ethanol. This reaction becomes possible only
when Mannich base ammonium salts are used as pre-
cursors of o-quinone methides in the presence of DBU
or other bases [25].
aldehyde, 33% aqueous dimethylamine, and naphtha-
len-2-ol (compounds Ia–Ic) [26, 27] or 6-(1-adaman-
tyl)naphthalen-2-ol (Ij) [28] in ethanol.
Compounds Id–Ii were synthesized in a similar
way.
1-[(1-Benzyl-1H-imidazol-5-yl)(dimethylamino)-
methyl]naphthalen-2-ol (Ih). Naphthalen-2-ol, 3 g
(0.021 mol), was dissolved in 15 ml of ethanol, 3.5 g
(0.026 mol) of 33% aqueous dimethylamine and 3.9 g
(0.021 mol) of 1-benzyl-1H-imidazole-5-carbaldehyde
[29] were added, and the mixture was kept for 48 h at
room temperature and for 2 h at –20°C. The precipitate
was filtered off, washed with ice-cold methanol, and
recrystallized from hot chloroform with addition of
petroleum ether. Yield 5.4 g (72%), mp 227−229°C.
IR spectrum, ν, cm–1: 3100−2500 (OH), 1624, 1601,
1582, 1520, 1470, 1412, 1373, 1269, 1238, 1223,
Compounds IIa–IIj characteristically displayed in
the IR spectra absorption bands in the region 2100–
2200 cm–1 due to stretching vibrations of conjugated
cyano group.
1
1115, 953, 833, 710. H NMR spectrum (CDCl3), δ,
ppm: 2.33 br.s [6H, (CH3)2N], 5.16 s (1H, CH), 5.29 s
(2H, CH2), 6.93–6.96 m (2H, Harom), 7.02 d (1H, Harom
,
J = 9.2 Hz), 7.07–7.11 m (1H, Harom), 7.15−7.30 m
(6H, Harom), 7.41 s (1H, Harom), 7.57 d (1H, Harom, J =
8.7 Hz), 7.63 d (1H, Harom, J = 7.8 Hz), 13.16 br.s (1H,
OH). 13C NMR spectrum (CDCl3), δC, ppm: 43.7
(CH3), 49.2 (CH), 61.4 (CH2), 113.6, 120.1, 120.7,
122.5, 126.5, 127.0, 128.3, 128.7, 128.9, 129.1, 130.0,
130.2, 131.8, 131.9, 135.7, 139.3, 155.0. Found, %:
C 77.35; H 6.54; N 11.69. C23H23N3O. Calculated, %:
C 77.28; H 6.49; N 11.76.
EXPERIMENTAL
The IR spectra were recorded in KBr on
a Shimadzu FTIR-8400S spectrometer. The H NMR
1
spectra were measured on a JEOL JNM-ECX400 spec-
trometer (400 MHz) from solutions in CDCl3 using
tetramethylsilane as internal reference. The mass
spectra (electron impact, 70 eV) were obtained on
a Finnigan Trace DSQ instrument. The elemental com-
positions were determined on a EuroVector EA-3000
automatic CHNS analyzer. Previously described Man-
nich bases were synthesized from the corresponding
1-[(Dimethylamino)(3-nitrophenyl)methyl]-
naphthalen-2-ol (Id). Yield 80%, mp 149−150°C
(from MeOH). IR spectrum, ν, cm–1: 3100−2500 (OH),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

OSIPOV et al.
400
1620, 1601, 1528 (NO2), 1470, 1354 (NO2), 1269,
1238, 1188, 957, 814. H NMR spectrum (CDCl3), δ,
131.9, 149.1, 150.5, 155.5. Found, %: C 77.74; H 6.47;
N 9.98. C18H18N2O. Calculated, %: C 77.67; H 6.52;
N 10.06.
1
ppm: 2.38 br.s [6H, (CH3)2N], 5.12 s (1H, CH), 7.19 d
(1H, Harom, J = 8.7 Hz), 7.36 d.d.d (1H, Harom, J = 7.8,
6.9, 0.9 Hz), 7.41−7.45 m (2H, Harom), 7.69−7.73 m
(2H, Harom), 7.83 d (1H, Harom, J = 8.5 Hz), 7.98 d (1H,
Harom, J = 7.8 Hz), 8.07 d.d.d (1H, Harom, J = 8.2, 2.3,
0.9 Hz), 8.46 d (1H, Harom, J = 1.9 Hz), 13.38 br.s (1H,
OH). 13C NMR spectrum (CDCl3), δC, ppm: 44.7
(CH3), 72.1 (CH), 115.3 (Carom), 120.2 (CHarom), 120.5
(CHarom), 122.9 (CHarom), 123.3 (CHarom), 123.8
(CHarom), 127.0 (CHarom), 128.8 (Carom), 129.2 (CHarom),
130.2 (CHarom), 130.3 (CHarom), 131.9 (Carom), 134.8
(CHarom), 142.7 (Carom), 148.4 (Carom), 155.4 (Carom).
Found, %: C 70.85; H 5.59; N 8.74. C19H18N2O3. Cal-
culated, %: C 70.79; H 5.63; N 8.69.
1-[(Dimethylamino)(thiophen-2-yl)methyl]naph-
thalen-2-ol (Ig). Yield 80%, mp 138−140°C (from
MeOH). IR spectrum, ν, cm–1: 3100–2300 (OH), 1620,
1597, 1470, 1323, 1265, 1238, 1188, 1157, 945, 818,
1
729. H NMR spectrum (CDCl3), δ, ppm: 2.39 br.s
[6H, (CH3)2N], 5.30 s (1H, CH), 6.86 d.d (1H, Harom
,
J = 5.0, 3.7 Hz), 7.14–7.21 m (2H, Harom), 7.26 t (1H,
Harom, J = 7.3 Hz), 7.42 d.d (1H, Harom, J = 8.4,
7.3 Hz), 7.68 d (1H, Harom, J = 9.2 Hz), 7.33 d (1H,
Harom, J = 8.2 Hz), 7.92 d (1H, Harom, J = 8.7 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 66.8 (CH),
116.6, 120.0, 120.9, 122.6, 125.8, 126.5, 126.7, 127.0,
128.7, 129.1, 129.9, 132.0, 143.3, 155.1. Found, %:
C 71.94; H 6.11; N 5.04; S 11.40. C17H17NOS. Cal-
culated, %: C 72.05; H 6.05; N 4.94; S 11.32.
1-[(Dimethylamino)(2-fluorophenyl)methyl]-
naphthalen-2-ol (Ie). Yield 80%, mp 137−139°C
(from MeOH). IR spectrum, ν, cm–1: 3000−2500 (OH),
1624, 1601, 1520, 1480, 1450, 1269, 1242, 1092, 953,
1-[(4-Chlorophenyl)(dimethylamino)methyl]-
naphthalen-2-ol (Ii). Yield 80%, mp 138−140°C
(from MeOH). IR spectrum, ν, cm–1: 3100–2300 (OH),
1620, 1597, 1470, 1323, 1265, 1238, 1188, 1157, 945,
1
825, 764. H NMR spectrum (CDCl3), δ, ppm: 2.26 s
and 2.56 s [6H, (CH3)2N], 5.58 s (1H, CH), 7.01 t (1H,
Harom, J = 7.3 Hz), 7.09 t (1H, Harom, J = 9.2 Hz),
7.16−7.23 m (2H, Harom), 7.26 t (1H, Harom, J =
7.3 Hz), 7.42 d.d.d (1H, Harom, J = 8.7, 6.9, 1.4 Hz),
1
818, 729. H NMR spectrum (CDCl3), δ, ppm:
2.34 br.s [6H, (CH3)2N], 4.96 s (1H, CH), 7.16 d (1H,
Harom, J = 9.2 Hz), 7.22–7.26 m (3H, Harom), 7.38 d.d.d
7.64 t.d (1H, Harom, J = 7.8, 1.4 Hz), 7.72 d (1H, Harom
,
(1H, Harom, J = 8.7, 6.9, 1.4 Hz), 7.52 d.d (2H, Harom
,
J = 9.2 Hz), 7.73 d (1H, Harom, J = 7.3 Hz), 7.85 d (1H,
Harom, J = 8.2 Hz). 13C NMR spectrum (CDCl3), δC,
ppm: 41.8 (CH3), 45.5 (CH3), 62.9 (CH), 115.3 d
(CHarom, J = 22.9 Hz), 115.6 (Carom), 120.1 (CHarom),
121.0 (CHarom), 122.7 (CHarom), 125.3 (CHarom), 126.8
(CHarom), 127.2 d (Carom, J = 12.4 Hz), 128.7 (Carom),
128.9 (CHarom), 129.9 d (CHarom, J = 8.6 Hz), 129.9
(CHarom), 130.2 (CHarom), 132.4 (Carom), 156.3 (Carom),
160.4 d (CF, J = 244.1 Hz). Found, %: C 77.30;
H 6.20; N 4.66. C19H18FNO. Calculated, %: C 77.27;
H 6.14; N 4.74.
J = 6.9, 1.4 Hz), 7.68 d (1H, Harom, J = 9.2 Hz), 7.71 d
(1H, Harom, J = 7.8 Hz), 7.79 d (1H, Harom, J = 8.7 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 45.0 (CH3),
72.2 (CH), 115.9, 120.1, 120.8, 122.6, 126.6, 128.8,
129.1, 129.9, 130.2, 132.0, 133.9, 138.9, 155.4. Found,
%: C 73.14; H 5.88; N 4.55. C19H18ClNO. Calculated,
%: C 73.19; H 5.82; N 4.49.
3-Amino-1-(1-benzyl-1H-imidazol-5-yl)-1H-
benzo[f]chromene-2-carbonitrile (IIh). A mixture of
2 g (5.6 mmol) of Mannich base Ih and 0.37 g
(5.6 mmol) of malononitrile in 10 ml of ethanol was
heated for 1 h under reflux and was then kept at
−20°C. The colorless precipitate was filtered off,
washed with ice-cold ethanol, and recrystallized from
EtOH–DMF. Yield 1.78 g (84%), mp 246−248°C
(decomp.). IR spectrum, ν, cm–1: 3500−2800 (NH2),
2183 (CN), 1655, 1589, 1412, 1234, 1084, 1049, 825,
1-[(Dimethylamino)(pyridin-4-yl)methyl]naph-
thalen-2-ol (If). Yield 80%, mp 164−166°C (from
MeOH). IR spectrum, ν, cm–1: 2800–2400 (OH), 1620,
1597, 1578, 1470, 1412, 1238, 949, 814, 752. 1H NMR
spectrum (CDCl3), δ, ppm: 2.37 br.s [6H, (CH3)2N],
4.96 s (1H, CH), 7.16 d (1H, Harom, J = 9.2 Hz),
7.25 d.d.d (1H, Harom, J = 7.8, 6.9, 0.9 Hz), 7.41 d.d.d
1
710. H NMR spectrum (DMSO-d6), δ, ppm: 5.27 s
(1H, Harom, J = 8.3, 6.9, 1.4 Hz), 7.52 d.d (2H, Harom
,
(1H, CH), 5.33 s (2H, CH2), 6.27 s (1H, Harom), 6.83 d
(1H, Harom, J = 8.5 Hz), 7.01–7.03 m (2H, Harom),
7.07 br.s (2H, NH2), 7.08–7.11 m (1H, Harom), 7.17 d
(1H, Harom, J = 8.9 Hz), 7.28–7.34 m (4H, Harom),
7.63 s (1H, Harom), 7.79 d (2H, Harom, J = 8.9 Hz).
13C NMR spectrum (DMSO-d6), δC, ppm: 48.6 (CH),
J = 4.6, 1.4 Hz), 7.69 d (1H, Harom, J = 8.7 Hz), 7.71 d
(1H, Harom, J = 8.3 Hz), 7.81 d (1H, Har1o3m, J = 8.7 Hz),
8.50 d.d (2H, Harom, J = 4.6, 1.4 Hz). C NMR spec-
trum (CDCl3), δC, ppm: 44.3 (CH3), 71.9 (CH), 115.0,
120.1, 120.6, 122.8, 123.5, 126.8, 128.8, 129.2, 130.3,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

NEW SYNTHESIS OF 3-AMINO-1H-BENZO[f]CHROMENE-2-CARBONITRILES
401
55.9 (CH2), 114.0, 117.1, 121.5, 123.3, 125.3, 127.4,
127.5, 127.9, 128.3, 128.9, 129.2, 130.2, 130.4, 131.2,
135.0, 137.3, 139.4, 147.5, 161.2, 161.3. Found, %:
C 76.23; H 4.71; N 14.87. C24H18N4O. Calculated, %:
C 76.17; H 4.79; N 14.81.
facilities of the Joint Use Center “Investigation of
Physicochemical Properties of Substances and
Materials.”
REFERENCES
Compounds IIa–IIg, IIi, and IIj were synthesized
in a similar way.
1. Shanthi, G., Perumal, P.T., Rao, U., and Sehgal, P.K.,
Indian J. Chem., Sect. B, 2009, vol. 48, p. 1319.
3-Amino-1H-benzo[f]chromene-2-carbonitrile
(IIa). Yield 76%, mp 209−211°C [25].
2. Ambler, S.J. Heath, W.F. Singh, J.P., Smith, C.W., and
Stramm, L.E., EU Patent no. 619314; Chem. Abstr.,
1995, vol. 122, no. 31327.
3-Amino-1-phenyl-1H-benzo[f]chromene-2-car-
bonitrile (IIb). Yield 90%, mp 279−281°C [20].
3. Kumar, A., Sharma, S., Maurya, R.A., and Sarkar, J.,
J. Comb. Chem., 2010, vol. 12, p. 20.
3-Amino-1-(4-methoxyphenyl)-1H-benzo[f]chro-
mene-2-carbonitrile (IIc). Yield 72%, mp 195−
196°C [20].
4. Kidwai, M., Saxena, S., Khanb, M.K.R., and
Thukral, S.S., Bioorg. Med. Chem. Lett., 2005, vol. 15,
p. 4295.
5. Zhou, D., Ren, Z., Cao, W., Chen, J., and Deng, H.,
J. Heterocycl. Chem., 2008, vol. 45, p. 1865.
6. Shestopalov, A.M., Emel’yanova, Yu.M., and Neste-
rov, V.N., Izv. Akad. Nauk, Ser. Khim., 2002, p. 2079.
7. Balalaie, S., Ramezanpour, S., Bararjanian, M., and
3-Amino-1-(3-nitrophenyl)-1H-benzo[f]chro-
mene-2-carbonitrile (IId). Yield 79%, mp 234−
235°C; published data [7]: mp 239−241°C.
3-Amino-1-(2-fluorophenyl)-1H-benzo[f]chro-
mene-2-carbonitrile (IIe). Yield 89%, mp 278−279°C
(decomp.); published data [7]: mp 294−295°C.
Gross, J.H., Synth. Commun., 2008, vol. 38, p. 1078.
8. Kumar, B.S., Srinivasulu, N., Udupi, R.H., Rajitha, B.,
Reddy, Y.T., Reddy, P.N., and Kumar, P.S., J. Hetero-
cycl. Chem., 2006, vol. 43, p. 1691.
9. Heravi, M.M., Bakhtiari, K., Zadsirjan, V., Bamo-
harram, F.F., and Heravi, O.M., Bioorg. Med. Chem.
Lett., 2007, vol. 17, p. 4262.
3-Amino-1-(pyridin-4-yl)-1H-benzo[f]chromene-
2-carbonitrile (IIf). Yield 85%, mp 246−248°C
(decomp.); published data [30]: mp 261−262°C.
3-Amino-1-(thiophen-2-yl)-1H-benzo[f]chro-
mene-2-carbonitrile (IIg). Yield 79%, mp 257−258°C
(decomp.) [31].
10. Jin, T.-S., Zhang, J.-S., Liu, L.-B., Wang, A.-Q., and
Li, T.-S., Synth. Commun., 2006, vol. 36, p. 2009.
3-Amino-1-(4-chlorophenyl)-1H-benzo[f]chro-
mene-2-carbonitrile (IIi). Yield 79%, mp 211−
212°C [30].
11. Kamdar, N.R., Haveliwala, D.D., Mistry, P.T., and
Patel, S.K., Eur. J. Med. Chem., 2010, vol. 45, p. 5056.
12. Ballini, R., Bosica, G., Conforti, M.L., Maggi, R., Maz-
zacani, A., Righic, P., and Sartorib, G., Tetrahedron,
2001, vol. 57, p. 1395.
13. Jin, T.-S., Xiao, J.-C., Wang, S.-J., Li, T.-S., and
Song, X.-R., Synlett, 2003, p. 2001.
14. Lu, G.-P. and Cai, C., J. Heterocycl. Chem., 2011,
8-(Adamantan-1-yl)-3-amino-1H-benzo[f]chro-
mene-2-carbonitrile (IIj). Yield 74%, mp 268−269°C
(decomp.). IR spectrum, ν, cm–1: 3429 (NH2), 3329
(NH2), 2903 (CH, Ad), 2847 (CH, Ad), 2181 (CN),
1651, 1593, 1416, 1240, 1080, 802. 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.71 s (6H, CH2, Ad), 1.90 s (6H,
CH2, Ad), 2.04 s (3H, CH, Ad), 3.71 s (2H, CH2),
6.83 s (2H, NH2), 7.10 d (1H, Harom, J = 8.7 Hz),
vol. 48, p. 124.
15. El-Agrody, A.M., Eid, F.A., Emam, H.A., Moha-
med, H.M., and Bedair, A.H., Z. Naturforsch., Teil B,
2002, vol. 57, p. 579.
16. Elagamey, A.G.A., El-Taweel, F.M.A., Sowel-
lim, S.Z.A., Sofan, M.A., and Elnagdi, M.H., Collect.
Czech. Chem. Commun., 1990, vol. 55, p. 524.
17. Sharanin, Yu.A. and Klokol, G.V., Zh. Org. Khim., 1982,
vol. 18, p. 2005.
18. Zhang, A.-Q., Zhang, M., Chen, H.-H., Chen, J., and
7.63 d (1H, Harom, J = 8.7 Hz), 7.71−7.73 m (2H,
13
H
arom), 7.79 d (1H, Harom, J = 9.2 Hz). C NMR spec-
trum (DMSO-d6), δC, ppm: 22.2 (CH2, Ad), 28.8 (CH,
Ad), 36.3 (C, Ad), 36.7 (CH2, Ad), 43.0 (CH2), 49.8,
111.9, 116.9, 121.8, 123.3, 123.7, 125.8, 129.3, 129.5,
130.8, 146.3, 148.0, 160.8. Found, %: C 80.93;
H 4.67; N 7.81. C24H24N2O2. Calculated, %: C 80.87;
H 6.79; N 7.86.
Chen, H.-Y., Synth. Commun., 2007, vol. 37, p. 231.
19. Shanthi, G. and Perumal, P.T., Tetrahedron Lett., 2007,
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 14.V37.21.1917) using
vol. 48, p. 6785.
20. Wang, X.-S., Yanga, G.-S., and Zhao, G., Tetrahedron:
Asymmetry, 2008, vol. 19, p. 709.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

OSIPOV et al.
402
21. Kumar, R., Nandi, G.C., Verma, R., and Singh, M.S.,
27. Monti, S.A. and Castillo, G.D., Jr., J. Org. Chem., 1970,
Tetrahedron Lett., 2010, vol. 51, p. 442.
vol. 35, p. 3764.
22. Nandi, G.C., Samai, S., and Singh, M.S., Synlett, 2010,
28. Osyanin, V.A., Ivleva, E.A., and Klimochkin, Yu.N.,
p. 1133.
Synth. Commun., 2012, vol. 42, p. 1832.
23. Fringuelli, F., Piermatti, O., and Pizzo, F., Synthesis,
29. Aulaskari, P., Ahlgrén, M., Rouvinen, J., Vainiotalo, P.,
Pohjala, E., and Vepsäläinen, J., J. Heterocycl. Chem.,
1996, vol. 33, p. 1345.
2003, p. 2331.
24. Osyanin, V.A., Osipov, D.V., and Klimochkin, Yu.N.,
Khim. Geterotsikl. Soedin., 2011, p. 1750.
25. Osyanin, V.A., Osipov, D.V., and Klimochkin, Yu.N.,
30. Meng, X.-Y., Wang, H.-J., Wang, Ch.-P., and
Zhang, Zh.-H., Synth. Commun., 2011, vol. 41, p. 3477.
Tetrahedron, 2012, vol. 68, p. 5612.
31. Abdel-Latif, F.F., Indian J. Chem., Sect. B, 1990,
26. Brode, W.R. and Littman, J.B., J. Am. Chem. Soc., 1931,
vol. 53, p. 1531.
vol. 29, p. 664.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013