Study of plant coumarins: X*.peurutenicin trifl ate in cross-coupling reactions

Article abstract of DOI:10.1134/S1070428012080106

By Suzuki cross-coupling reaction of peurutenicin trifl ate with arylboric, furanylboric, pyridinylboric, and indolylboric acids the corresponding 7-aryl(hetaryl)coumarins were synthesized. The high activity of hetarylsubstituted boric acids in the Suzuki

Full text of DOI:10.1134/S1070428012080106

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 8, pp. 1094−1102. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.A. Makhneva, A.V. Lipeeva, E.E. Shults, M.M. Shakirov, G.A. Tolstikov, 2012, published in Zhurnal Organicheskoi Khimii, 2012,
Vol. 48, No. 8, pp. 1097−1105.
Study of Plant Coumarins: X*.
Peurutenicin Triflate in Cross-Coupling Reactions
E. A. Makhnevaa,b, A. V. Lipeevaa, E. E. Shultsa, M. M. Shakirova, and G. A. Tolstikova
aVorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
e-mail: schultz@nioch.nsc.ru
bNovosibirsk State University, Novosibirsk, Russia
Received January 31, 2012
Abstract—By Suzuki cross-coupling reaction of peurutenicin triflate with arylboric, furanylboric, pyridinylboric,
and indolylboric acids the corresponding 7-aryl(hetaryl)coumarins were synthesized. The high activity of hetaryl-
substituted boric acids in the Suzuki reaction was observed. Heck reaction of 7-O-trifluoromethylsulfonylpeur
utenicin with terminal olefins (styrene, vinylpyridines, vinylpyrazine, vinyltriazole) was used to prepare (Е)-7-
[aryl(hetaryl)vinyl]coumarins. The dependence of reaction products yield on the nature of the catalytic system
was found.
DOI: 10.1134/S1070428012080106
Peurutenicin [7-hydroxy-6-(methoxycarbonyl)
coumarin] (I) is produced by various plant species of
genus Peucedanum (hog’s fennel) [2]. Its structure was
unambiguously established from the product of its alka-
line hydrolysis (umbelliferone-6-carboxylic acid), and
also by an independent synthesis [3]. We described in [4]
an efficient procedure of the preparation of peurutenicin
(I) from peucedanine (II), a metabolite of Peucedanum
morisonii. The availability of compound I, and also the
known pharmacological activity of the functionally sub-
stituted coumarins arouse our interest in the investigation
of its transformations, in particular, in the preparation of
7-substituted derivatives.
Coumarins with diverse substituents in the position С7
are extensively studied because of their antibacterial and
fungicidal action [5], their effect on aromatase [6] and
monoamine oxides А and B [7], providing the potential
of these compounds in the treatment of neurodegenera-
tive diseases. 7-Aryl-substituted coumarins are regarded
as a new group of selective nonsteroid inhibitors of
hydroxysteroid 17-β- dehydrogenase of the first type [8].
of the appropriate 7-formyl derivatives [9] or by the
conversion of 3-styrylphenols [7]. In the synthesis of
7-(indol-3-yl)coumarins a Pd-catalyzed reaction of um-
belliferone triflate with o-alkynyl-trifluoroacetanilides
was used [10]. Suzuki–Miyaura reactions were described
involving 4-trifluoromethylsulfonyloxycoumarins afford-
ing 4-aryl(hetaryl)coumarins [11], and also 7-trifluoro-
methylsulfonyloxycoumarins providing 7-arylcoumarins
[8]. 7-Trifluoromethylsulfonyloxycoumarins were not
brought into Heck reaction.
The aim of this study was the synthesis of peurutenicin
derivatives with aromatic, heterocyclic, or styryl and
hetarylvinyl substituents in the position С7 using Pd-
catalyzed cross-coupling of peurutenicin triflate (III) with
boric acids (Suzuki– Miyaura reaction) or with terminal
olefins (Heck reaction).
7-O-Trifluoromethylsulfonylpeurutenicin (III)
formed in the reaction of peurutenicin (I) with
trifluoromethanesulfonic anhydride in pyridine (yield
77%) (Scheme 1).
The reaction of triflate III with arylboric acids IV, V in
dioxane in the presence of the complex Pd(PPh3)4 widely
used in the Suzuki coupling and 3 equiv of K2CO3, and
also of 10 mol% of Bu4N+Br– led to the formation of the
Styrylcoumarins were obtained by Wittig reaction
_______________
* For Communication IX, see [1]
1094

STUDY OF PLANT COUMARINS: X
1095
Scheme 1.
O
MeO
O
(1) m-ClC6H4CO3H, CHCl3
(2) NaOH, MeOH_H2SO4
Tf2O_Py
4
5
MeO
TfO
6
7
MeO
HO
3
2
8
O
O
O
O
O
O
O
III
I
II
acids XIV, XV gave 7-(pyridin-4-yl)coumarins XVI,
XVII in a high yield.
products of coumarin arylation VI, VII (Scheme 2). The
attempt to react triflate III with 2-aminophenylboric acid
(V) in acetonitrile using as a catalyst complex PdCl2(dppf)
[dppf is a bidentate ligand 1,1'-bis(diphenylphosphino)
ferrocene) under the conditions utilized in [12] has not
increased the yield of the reaction product. The cross-
coupling of triflate III with indole-5-boric acid (VIII) in
the presence of Pd(PPh3)4 made it possible to synthesize
coumarin derivative IX with an indole fragment in the
position С7. The reaction of peurutenicin triflate (III) with
3-furanboric acid (Х) or 2-furanboric acid (XI) furnished
the corresponding 6-methoxycarbonyl-7-(furan-2-yl)-
(XII) or 6-methoxycarbonyl-3-(furan-3-yl)coumarins
(XIII). The reactions of triflate III with pyridineboric
Thus by the Suzuki reaction of peurutenicin triflate
(III) with aryl(hetaryl)boric acids we synthesized versa-
tile compounds, among them combining in the structure
the fragments of coumarin and the other heterocyclic
compounds (indole, furan, or pyridine).
We investigated the possibility to use Heck reaction of
triflate III with vinylpyridines XVIII, XIX for the syn-
thesis of 7-(pyridin-4-ylvinyl)-substituted peurutenicin
(I) derivatives. The reaction conditions were chosen by
an example of triflate III interaction with 2-vinylpyridine
(XVIII). The reaction was first carried out in DMF using
a catalyst system Pd(OAc)2–(o-tol)3P (2/8 mol%) in the
Scheme 2.
B(OH)2
O
R2
O
B(OH)2
MeO
MeO
N
R1
H
IV, V
VIII
O
O
O
O
III
4'
5'
6'
5'
4'
a
1'
2'
3'
a,
b
R2
R1
3
'
6
'
7'
1'
N
VI, VII, 55%
IX, 79%
H
O
O
B(OH)2
(HO)2B
MeO
O
MeO
O
4'
N
3'
2'
O
X
O
O
XIV
6'
5'
O
a
a,
b
XII, 44%
1'
N
B(OH)2
XVI, 77%
III
B(OH)2
O
O
N
O
a
a
XV
XI
MeO
MeO
5'
6'
O
O
O
O
O
4'
3'
N
1'
2'
XVII, 82%
XIII, 45%
R1 = Cl, R2 = CF3 (IV, VI); R1 = NH2, R2 = H (V, VII). (a) Pd(PPh3)4, K2CO3, Bu4NBr, dioxane, 100°C; (b) PdCl2(dppf),
K2CO3, Bu4NBr, MeCN, 80°C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

MAKHNEVA et al.
1096
The structure and composition of compounds
synthesized was established from the spectral data and
elementalanalyses. 1Нand13СNMRspectraofcompounds
obtained contain one set of characteristic signals of
the coumarin framework and of the corresponding
substituent. The protons of the double bond Ha,b in the
1Н NMR spectra of compounds XX, XXI, XXIV, XXV,
XXVII give rise to doublets in the region 8.42–8.05,
6.88 or 7.50–7.04, 6.74 ppm. The spin-spin coupling
constant between the protons Ha,b in the 1Н NMR spectra
of compounds XX, XXI, XXIV, XXV (J 15.8–16.6 Hz)
and (XXVII) (J 14.8 Hz) indicates their trans-position.
presence of triethylamine (115°С, 7 h), under the condi-
tions of reaction of vinylpyridine XVIII with furocou-
marin oreoselone triflate [13], but the process required
more stringent conditions (135–140°С, 10–16 h). The
conversion of triflate III and the reaction product yield
grew with increased charge of the palladium source,
4/8 mol% of Pd(OAc)2–(o-tol)3P. The reaction of triflate
III with 2-vinylpyridine (XVIII) was carried out over
16 h in the presence of the catalytic system Pd(OAc)2–
(o-tol)3P(4/8 mol%), the conversion of triflate III reached
66%. The complete conversion of initial compound III
was obtained at the use BINAP as the ligand; the yield
of (E)-[7-(pyridin-2-yl)vinyl]coumarin (XX) was 75%
(Scheme 3). By the reaction of triflate III with 5-vinyl-
2-methylpyridine (XIX) (E)-[7-(pyridin-2-yl)vinyl]
coumarin (XXI) was obtained. The reaction of triflate III
with 2-vinylpyrazine (XXII) or 1-vinyl-1H-1,2,4-triazole
(XXIII) resulted in individual (E)-7-pyrazinylvinyl- or
(E)-7-triazolylvinyl-6-methoxycarbonyl-2Н-chromen-2-
ones (ХХIV, XXV). In the reaction of peurutenicin triflate
(III) with styrene (ХХVI) in the presence of the catalytic
system Pd(OAc)2–BINAP (4/8 mol%) we isolated only
7-styrylcoumarin (ХХVII).
Therefore the Pd-catalyzed reactions of peurutenicin
triflate with aryl(hetaryl)boric acids or with terminal
alkenes provide new opportunities of peurutenicin
modification and permit syntheses of versatile coumarins
substituted at the С7 atom that may possess valuable
pharmacological properties.
EXPERIMENTAL
NMR spectra from solutions of compounds in
CDCl3 or in a mixture CDCl3 + CD3ОD (XII, XVII,
Scheme 3.
O
O
H2C
CH2
XVIII
a_e
MeO
MeO
N
XIX
N
a
a
III
O
O
O
O
e
N
1'
N
b
b
2'
1'
3'
2'
Me
4'
3'
4'
XX, 75%
XXI, 43%
N
N
O
O
N
N
CH2
MeO
MeO
N
N
XXIII
XXII
a
III
a
O
O
O
O
e
e
b
N
b
2'
1'N
1'
3'
PhCH=CH2
2'
3'
4'
e
4'
N
XXVI
XXV, 48%
XXIV, 56%
N
O
MeO
Ph
a
O
O
b
XXVII, 78%
Reagents and conditions: (а) Pd(OAc)2, (o-tol)3P, Et3N, DMF, 115°С, 7 h; (b) Pd(OAc)2, (o-tol)3P, Et3N, DMF, 135–140°С,
10 h; (c) Pd(OAc)2, (o-tol)3P, Et3N, DMF, 135–140°С, 10 h; (d) Pd(OAc)2, (o-tol)3P, Et3N, DMF, 135–140°С, 16 h; (e)
Pd(OAc)2, BINAP, Et3N, DMF, 135–140°С, 16 h.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

STUDY OF PLANT COUMARINS: X
1097
XXV) were registered on spectrometers Bruker AV-300
[300.13 (1Н) and 75.47 MHz (13С)], AV-400 [400.13
(1Н) and 100.78 MHz (13С)], and AV-600 [600.30 (1Н)
3087, 3059, 2960, 1744, 1725, 1630, 1431, 1226, 1135,
960, 870, 750, 658, 601. UV spectrum (EtOH), λmax
,
nm (log ε): 206 (3.99), 231 (4.11), 320 (4.06). 1Н NMR
spectrum, δ, ppm: 3.99 s (3H, OСH3), 6.29 d (1Н, Н3,
J 9.5 Hz), 6.87 s (1Н, Н8), 7.62 d (1Н, Н4, J 9.5 Hz),
8.01 s (1Н, Н5). 13С NMR spectrum, δ, ppm: 51.55
(OСH3), 104.09 s (C6), 108.10 d (С8), 113.52 d (С3),
113.88 s (С4а), 119.02, 120.23, 122.87, 125.32 s (CF3,
J 266.6 Hz), 133.38 d (С5), 144.35 d (C4), 152.18 s (С7),
158.41 s (C8a), 160.68 s (С2), 167.04 s (C=О). 19F NMR
spectrum, δ, ppm: 88.70 (СF3). Found, %: F 16.12; S 9.05.
С12Н7F3O7S. Calculated, %: F 16.18; S 9.10.
1
and 150.96 MHz (13С)]. Chemical shifts in the H and
13С NMR spectra were measured with respect to the resid-
ual signals of the solvent СНСl3 (δH 7.24, δC 76.90 ppm).
Chemical shifts in the 19F NMR spectra were measured
with respect to the internal reference C6F6. The multiplic-
ity of signal in the 13С NMR spectra were determined at
recording the spectra in the J modulation mode. IR spectra
were taken on a spectrophotometer Vector-22 from pel-
lets with KВr. UV absorption spectra were recorded on
a spectrometer HР 8453 UVVis. The melting points were
measured on a heating block Stuart SMF-38. Elemental
analysis was carried out on a СНN-analyzer Carlo Erba
1106. The reaction products were isolated by column
chromatography on silica gel Acros (0.035–0.070 mm),
eluents chloroform, chloroform–ethanol, 50:2. The reac-
tion progress was monitored by TLC on Silufol UV-254
plates, eluent chloroform–ethanol, 50:2. The spots were
visualized in the iodine chamber or under UV irradiation.
6-(Methoxycarbonyl)-7-[2-chloro-5-(trifluoro-
methyl)phenyl]-2H-chromen-2-one (VI). To a solution
of 100 mg (0.3 mmol) of peurutenicin triflate (III)
in 3 ml of dioxane under an argon atmosphere was
added at stirring in succession 90 mg (0.39 mmol) of
5-(trifluoromethyl)-2-chlorophenylboric acid (IV), 17 mg
(5 mol%) of Pd(PPh3)4, 7 mg (10 mol%) of Bu4NBr, and
123 mg (0.9 mmol) of K2CO3. The mixture was stirred
over 8 h at 100°С. On the completion of the reaction
(TLC monitoring) the reaction mixture was evaporated
to 1 ml, the residue was diluted with 5 ml of water, the
reaction product was extracted into dichloromethane (4 ×
5 ml), the combined extracts were dried with MgSO4.
The solvent was distilled off, the residue was chromato-
graphed on silica gel, the fraction containing the reaction
product was treated with ether. Yield 60 mg (52%), mp
144–145°С (from ether). IR spectrum, cm–1: 3450, 3380,
3118, 2953, 1740, 1729, 1644, 1608, 1473, 1416, 1198,
1220, 1137, 1105, 1040, 872, 743, 623. UV spectrum
(EtOH), λmax, nm (log ε): 208 (4.42), 241 (4.20), 276
(3.63), 286 (3.66), 311 (3.66). 1Н NMR spectrum, δ, ppm:
3.69 s (3H, OСH3), 6.52 d (1Н, Н3, J 9.6 Hz), 7.48 d (1Н,
Н3', J 8.8 Hz), 7.56 d.d (1Н, Н4', J 8.8, 1.9 Hz), 7.61 s (1Н,
Н8), 7.66 d (1Н, Н6', J 1.9 Hz), 7.81 d (1Н, Н4, J 9.6 Hz),
8.29 s (1Н, Н5). 13С NMR spectrum, δ, ppm: 51.80 q
(OСН3), 109.47 d (С8), 112.92 d (C3), 114.41 s (C4а),
121.33 s (C5'), 123.04 d (С4'), 125.83 q (CF3, J 285.4 Hz),
126.09 s (C6), 129.90 d (C5), 130.08 d (С6'), 131.70 d (С3'),
138.67 s (С7), 141.84 s (C2'), 142.95 s (C1'), 144.74 d (C4),
161.30 s (C2), 164.89 s (С8а), 166.40 s (C=O). Found,
%: C 57.02; H 2.73; Cl 916; F 14.70. С18Н10ClF3O4.
Calculated, %: С 56.49; H 2.63; Cl 9.26; F 14.89.
In the study was used PdCl2(dppf) from Alfa Aesar.
Pd(PPh3)4 was synthesized by procedure [14]. Arylboric
acids IV, V, hetероarylboric acids VIII, X, XI, XIV,
XV, and vinylarenes XVIII, XIX, XXII were bought
from Alfa Aesar.
The solvents (acetonitrile, dioxane, DMF), and also
Et3N were purified by standard procedures and distilled
in an argon flow just before reactions. Peurutenicin
[7-hydroxy-6-(methoxycarbonyl)coumarin] (I) was ob-
tained from peucedanine (II) as described in [4].
6-(Methoxycarbonyl)-7-(trifluoromethylsulfonyl-
oxy)-2H-chromen-2-one (III). A solution of 500 mg
(2.27 mmol) of peurutenicin (I) in 5 ml of pyridine was
cooled to 0°С and at stirring under an argon atmosphere
1.15 ml (6.81 mmol) of trifluoromethanesulfonic anhy-
dride was added within 30 min, the reaction mixture was
warmed to the room temperature and was left standing
for 48 h with intermittent stirring. On the completion of
the reaction (TLC monitoring by the disappearance of the
spot of compound I) the reaction mixture was quenched
with 10 ml of water, the reaction product was extracted
into ether (4 × 5 ml), the combined organic solvents were
dried with magnesium sulfate. The solvent was distilled
off in a vacuum, the traces of pyridine were removed
by azeotropic distillation with benzene, the residue was
crystallized from ethanol. Yield 585 mg (77%), mp
106–108°С (from ethanol). IR spectrum, cm–1: 3127,
7-(2-Aminophenyl)-6-(methoxycarbonyl)-2H-
chromen-2-one (VII). a. To a solution of 100 mg
(0.3 mmol) of peurutenicin triflate (III) in 3 ml of dioxane
under an argon atmosphere was added at stirring in suc-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

MAKHNEVA et al.
1098
was stirred for 12 h at 80°С (TLC monitoring), it was
evaporated to 1 ml and diluted with 5 ml of water. The
reaction product was extracted into dichloromethane (4 ×
5 ml), the combined extracts were dried with MgSO4.
The residue was subjected to chromatography on silica
gel, the fraction containing the reaction product was
treated with ether. Yield 38 mg (79%), mp 133–135°С
(from ether). IR spectrum, cm–1: 3393, 3222, 3080, 3061,
2964, 2925, 2852, 2702, 1735, 1676, 1626, 1600, 1579,
1510, 1491, 1446, 1430, 1342, 1299, 1234, 1214, 1145,
1109, 1076, 1064, 948, 915, 903, 826, 797, 735, 687.
UV spectrum (EtOH), λmax, nm (log ε): 202 (4.41), 226
(4.46), 245 (4.12), 288 (3.79), 300 (3.60), 325 (3.86).
1Н NMR spectrum, δ, ppm: 3.90 s (3H, OСH3), 6.20 d
(1Н, Н3, J 9.7 Hz), 6.59 d (1Н, H3', J 3.0 Hz), 7.15 d
(1Н, H2', J 3.0 Hz), 7.22 d (1Н, H7', J 8.4 Hz), 7.36 d
(1Н, H6', J 8.4 Hz), 7.50 s (1Н, H8), 7.68 s (1Н, Н4'),
7.78 d (1Н, H4, J 9.7 Hz), 7.94 s (1Н, Н4), 9.82 s (1H,
NH). 13С NMR spectrum, δ, ppm: 51.72 q (OСH3),
105.11 d (C3'), 108.75 d (C7'), 109.54 d (C8), 112.72 d
(С3), 113.40 d (С6'), 122.61 d (С4'), 123.75 s (С4а'),
125.90 s (С6), 126.70 d (C5), 134.31 d (C2), 136.47 s
(C3а'), 138.29 s (C7), 144.19 d (C4), 145.22 s (C7а'),
146.93 s (C5'), 161.24 s (C2), 162.72s (C8а), 165.67 s
(C=O). Found, %: C 71.93; H 3.99; N 4.27. С19Н13NO4.
Calculated, %: С 71.47; H 4.10; N 4.39.
cession 53 mg (0.39 mmol) of 2-aminophenylboric acid
(V), 17 mg (5 mol%) of Pd(PPh3)4, 7 mg (10 mol%) of
Bu4NBr, 123 mg (0.9 mmol) of K2CO3. The reaction
mixture was stirred over 8 h at 100°С, was evaporated
to 1 ml, the residue was diluted with 5 ml of water,
the reaction product was extracted into dichlorometh-
ane (4 × 5 ml), the combined extracts were dried with
MgSO4. The drying agent was filtered off, the solvent
was evaporated in a vacuum, the residue was subjected
to chromatography on silica gel, the fraction containing
the reaction product was treated with ether. Yield 50 mg
(55%), mp 139–140°С (from ether). IR spectrum, cm–1:
3448, 3395, 3320, 3233, 3128, 3061, 2857, 1744, 1727,
1677, 1630, 1612, 1584, 1504, 1430, 1331, 1297, 1223,
1137, 1102, 1060, 1033, 991, 961, 904. 884, 871, 843,
753, 655, 602. UV spectrum (EtOH), λmax, nm (log ε):
208 (4.42), 241 (4.20), 276 (3.63), 286 (3.66), 311 (3.66).
1Н NMR spectrum, δ, ppm: 3.73 s (2H, NH2), 3.93 s (3H,
OСH3), 6.15 d (1Н, Н3, J 9.6 Hz), 6.46 d.d (1Н, Н3', J 7.8,
1.2 Hz), 6.90 d.d.d (1Н, Н5', J 8.1, 7.6, 1.2 Hz), 6.95 d.d.d
(1Н, Н4', J 8.1, 7.8, 1.5 Hz), 7.46 d.d (1Н, Н6', J 7.6,
1.5 Hz), 7.52 s (1Н, Н8), 7.72 d (1Н, H4, J 9.6 Hz), 7.92 s
(1Н, Н5). 13С NMR spectrum, δ, ppm: 51.82 q (OСH3),
101.65 d (C8), 112.45 d (C3), 113.42 s (C4a), 117.02 s (C1'),
117.71 d (C5'), 119.93 d (C6'), 125.75 s (C6), 128.51 d (С5),
130.45 d (С6'), 139.59 s (С7), 143.33 s (С2'), 144.30 d (C4),
146.24 d (C4'), 160.22 s (C2), 164.79 s (C8а), 167.43 s
(C=O). Found, %: C 69.09; H 4.24; N 4.80. С17Н13NO4.
Calculated, %: С 69.15; H 4.44; N 4.74.
6-(Methoxycarbonyl)-7-(furan-3-yl)-2H-chromen-
2-one (XII). а. To a solution of 85 mg (0.26 mmol) of
peurutenicin triflate (III) in 3 ml of dioxane under an
argon atmosphere was added at stirring in succession
37 mg (0.33 mmol) of 3-furanboric acid (X), 15 mg
(5 mol%) of Pd(PPh3)4, 6 mg (10 mol%) of Bu4NBr,
104 mg (0.78 mmol) of K2CO3. The reaction mixture
was stirred for 8 h at 100°С, cooled, it was evaporated
in a vacuum to 1 ml and diluted with 5 ml of water. The
reaction product was extracted into dichloromethane (4 ×
5 ml), the combined extracts were dried with MgSO4.
The residue was subjected to chromatography on silica
gel. Yield 36 mg (44%), mp 123–125°С (from ether). IR
spectrum, cm–1: 3316, 2945, 2857, 2797, 1744, 1727,
1678, 1630, 1607, 1565, 1503, 1431, 1378, 1329, 1300,
1225, 1205, 1140, 1099, 1064, 1019, 960, 933, 904, 878,
840, 827, 773, 750, 685, 657, 602. UV spectrum (EtOH),
b. To a solution of 100 mg (0.3 mmol)of
peurutenicin triflate (III) in 3 ml of acetonitrile under
an argon atmosphere was added 53 mg (0.39 mmol)
of 2-aminophenylboric acid (V), 11 mg (5 mol%) of
PdCl2(dppf), 7 mg (10 mol%) of Bu4NBr, 123 mg
(0.9 mmol) of K2CO3. The reaction mixture was stirred
for 12 h at 80°С, it was evaporated to 1 ml and diluted
with 5 ml of water. The reaction product was extracted
into dichloromethane (4 × 5 ml). The residue was chro-
matographed on silica gel, trace amount of the reaction
product was isolated insufficient for further analysis, and
85 mg of the initial triflate.
7-(1H-Indol-5-yl)-6-(methoxycarbonyl)-2H-
chromen-2-one (IX). To a solution of 50 mg (0.15 mmol)
of peurutenicin triflate (III) in 3 ml of acetonitrile under
an argon atmosphere was added at stirring in succession
32 mg (0.2 mmol) of 5-indolylboric acid (VIII), 8.5 mg
(5 mol%) of Pd(PPh3)4, 3.5 mg (10 mol%) of Bu4NBr,
and 62 mg (0.45 mmol) of K2CO3. The reaction mixture
λ
max, nm (log ε): 203 (4.15), 240 (3.85), 275 (3.38), 285
(3.35), 312 (3.24). 1Н NMR spectrum, δ, ppm: 3.93 s (3H,
OСH3), 6.48 d (1Н, Н3, J 9.6 Hz), 6.51 d.d (1Н, Н4', J 3.6,
1.6 Hz), 7.25 s (1Н, Н8), 7.48 d.d (1Н, Н5', J 3.6, 1.8 Hz),
7.65 d (1Н, Н2', J 1.6 Hz), 7.75 d (1Н, Н4, J 9.6 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

STUDY OF PLANT COUMARINS: X
1099
8.24 s (1Н, Н5). 13С NMR spectrum, δ, ppm: 52.93 q
(OСH3), 111.80 d (C8), 113.19 d (С3), 118.33 d (С4'),
118.46 s (С4a), 120.67 s (C6), 128.17 s (C3'), 132.64 d
(C5), 137.87 s (C7), 139.65 d (C5'), 141.91 d (C4), 142.52 d
(C2'), 156.60 s (C8а), 158.64 s (C2), 162.98 s (C=O).
Found, %: С 67.93; Н 3.99. С15Н10O5. Calculated, %:
С 67.67; H 3.83.
of peurutenicin triflate (III) in 3 ml of dioxane under an
argon atmosphere was added at stirring in succession
40 mg (0.33 mmol) of 3-pyridineboric acid (XIV), 15 mg
(5 mol%) of Pd(PPh3)4, 6 mg (10 mol%) of Bu4NBr, and
104 mg (0.78 mmol) of K2CO3. The reaction mixture
was stirred for 8 h at 100°С, cooled, evaporated in a
vacuum, the residue was diluted with 5 ml of water. The
reaction product was extracted into dichloromethane (4 ×
5 ml), the combined extracts were dried with MgSO4.
The residue was chromatographed on silica gel. Yield
60 mg (82%), mp 123–124°С (from ether). IR spectrum,
cm–1: 3060, 2956, 2924, 2854, 1728, 1674, 1627, 1600,
1582, 1491, 1452, 1431, 1394, 1375, 1346, 1299, 1278,
1236, 1224, 1180, 1140, 1101, 1074, 1061, 1010, 1001,
960, 943, 903, 870, 827, 796, 752, 721, 651, 599. UV
spectrum (EtOH), λmax, nm (log ε): 202 (4.19), 225
(4.14), 242 (4.19), 275 (3.66), 287 (3.70), 306 (3.72), 322
(3.73). 1Н NMR spectrum, δ, ppm: 3.99 s (3H, OСH3),
6.27 d (1Н, Н3, J 9.8 Hz), 6.87 s (1Н, Н8), 7.46 m (1Н,
Н5'), 7.50 d.d (1Н, Н4', J 7.7, 1.8 Hz), 7.53 d.d (1Н, Н6',
J 7.5, 1.8 Hz), 7.75 d (1Н, Н4, J 9.8 Hz), 8.01 s (1Н, Н5),
8.28 br.s (1Н, Н2'). 13С NMR spectrum, δ, ppm: 52.51 q
(OСH3), 104.85 d (C8), 114.14 d (С3), 119.26 s (С4a),
120.76 s (C6), 124.17 d (C5'), 130.64 d (C5), 132.00 s (C1'),
135.85 s (C7), 137.60 d (C6'), 142.94 d (C2'), 144.20 d (C4),
149.50 d (C4'), 160.04 s (C2), 164.26 s (C8а), 169.32 s
(C=O). Found, %: C 68.04; H 3.78; N 4.88. С16Н11NO4.
Calculated, %: С 68.32; H 3.94; N 4.98.
b. To a solution of 100 mg (0.3 mmol) of peurutenicin
triflate (III) in 3 ml of acetonitrile under an argon at-
mosphere was added at stirring in succession 43 mg
(0.39 mmol) of 3-furanboric acid (Х), 11 mg (5 mol%)
of PdCl2(dppf), 7 mg (10 mol%) of Bu4NBr, and 123 mg
(0.9 mmol) of K2CO3. The reaction mixture was stirred for
12 h at 80°С, it was evaporated to 1 ml and diluted with
5 ml of water. The reaction product was extracted into
dichloromethane (4 × 5 ml), the combined extracts were
dried with MgSO4. The residue was chromatographed on
silica gel. Yield 15 mg (18%).
6-(Methoxycarbonyl)-7-(furan-2-yl)-2H-chromen-
2-one (XIII). To a solution of 85 mg (0.26 mmol) of
peurutenicin triflate (III) in 3 ml of dioxane under an
argon atmosphere was added at stirring in succession
37 mg (0.33 mmol) of 2-furanboric acid (XI), 15 mg
(5 mol%) of Pd(PPh3)4, 6 mg (10 mol%) of Bu4NBr,
and 104 mg (0.78 mmol) of K2CO3. The reaction mix-
ture was stirred for 8 h at 100°С. On the completion of
the reaction (TLC monitoring) the reaction mixture was
evaporated, the residue was diluted with 5 ml of water.
The reaction product was extracted into dichloromethane
(4 × 5 ml), the combined extracts were dried with MgSO4.
The residue was chromatographed on silica gel. Yield
36 mg (44%), mp 130–132°С (from ether). IR spectrum,
cm–1: 2944, 2858, 1745, 1727, 1677, 1630, 1607, 1432,
1332, 1297, 1224, 1202, 1182, 1136, 1101, 1060, 1040,
960, 934, 904, 871, 835, 828, 794, 750, 683, 656, 630,
601. UV spectrum (EtOH), λmax, nm (log ε): 200 (4.00),
237 (4.01), 275 (3.39), 285 (3.36), 311 (3.24). 1Н NMR
spectrum, δ, ppm: 3.94 s (3H, OСH3), 6.37 br.s (1Н, Н4'),
6.50 d (1Н, Н3, J 9.6 Hz), 6.94 br.s (1Н, Н3'), 7.22 s (1Н,
Н8), 7.56 br.s (1Н, Н5'), 7.75 d (1Н, Н4, J 9.6 Hz), 8.24 s
(1Н, Н5). 13С NMR spectrum, δ, ppm: 51.71 q (OСH3),
104.99 d (C8), 107.26 d (C3'), 107.46 s (С4a), 108.97 d
(C4'), 112.52 d (С3), 113.80 s (C6), 123.32 d (C5), 138.38 s
(C7), 140.79 d (C4), 144.20 s (C2'), 152.87 d (C5'), 158.41 s
(C2), 161.68 s (C8а), 160.64 s (C=O). Found, %: C 66.46;
H 4.00. С15Н10O5. Calculated, %: С 66.67; H 3.73.
6-(Methoxycarbonyl)-7-(pyridine-4-yl)-2H-
chromen-2-one (XVII). To a solution of 85 mg
(0.26 mmol) of peurutenicin triflate (III) in 3 ml of di-
oxane under an argon atmosphere was added at stirring
in succession 40 mg (0.33 mmol) of 4-pyridineboric acid
(XV), 15 mg (5 mol%) of Pd(PPh3)4, 6 mg (10 mol%) of
Bu4NBr, and 104 mg (0.78 mmol) of K2CO3. The reaction
mixture was stirred for 8 h at 100°С, cooled, evaporated
in a vacuum, the residue was diluted with 5 ml of water.
The reaction product was extracted into dichloromethane
(4 × 5 ml), the combined extracts were dried with MgSO4.
The residue was chromatographed on silica gel. Yield
56 mg (77%), mp 143–144°С (from ether). IR spectrum,
cm–1: 3431, 3060, 2960, 1728, 1674, 1627, 1579, 1490,
1431, 1377, 1296, 1222, 1180, 1137, 1101, 1060, 960,
902, 871, 842, 750, 655, 599. UV spectrum (EtOH), λmax
,
nm (log ε): 213 (3.91), 219 (4.11), 222 (4.13), 225 (4.14),
244 (4.38), 276 (3.85), 287 (3.87), 323 (3.87), 338 (3.74).
1Н NMR spectrum, δ, ppm: 3.99 s (3H, OСH3), 6.30 d
(1Н, Н3, J 9.6 Hz), 6.61 d (1Н, Н3',5', J 7.5 Hz), 6.75 s
6-(Methoxycarbonyl)-7-(pyridine-3-yl)-2H-
chromen-2-one(XVI).Toasolutionof85mg(0.26mmol)
(1Н, Н8), 7.75 d (1Н, Н4, J 9.6 Hz), 7.81 d (1Н, Н2',6'
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

MAKHNEVA et al.
1100
J 7.5 Hz), 8.08 s (1Н, Н5). 13С NMR spectrum, δ, ppm:
52.32 q (OСH3), 104.05 d (C8), 113.16 d (С3), 117.88 d
(C3',5'), 118.37 s (С4a), 120.31 s (C6), 130.69 d (C5),
132.47 s (C7), 142.05 d (C4), 143.44 d (C2'), 146.53 d (C6'),
156.36 s (C1'), 161.75 s (C2), 163.50 s (C8а), 168.94 s
(C=O). Found, %: C 67.94; H 4.08; N 4.86. С16Н11NO4.
Calculated, %: С 68.32; H 3.94; N 4.98.
of NEt3. The reaction mixture was stirred for 10 h at
135–140°С and poured in a Petri dish. On evaporation of
the solvent the residue was subjected to column chroma-
tography on silica gel (eluent chloroform) to isolate 50 mg
(75%) of the reaction product, conversion of triflate 47%.
e. To a solution of 150 mg (0.46 mmol) of peurutenicin
triflate (III) in 3 ml of DMF under an argon atmosphere
was added at stirring in succession 97.2 mg (0.93 mmol)
of 2-vinylpyridine (XVIII), 4 mg (4 mol%) of Pd(OAc)2,
11 mg (8 mol%) of (о-tol)3P, and 0.064 ml (0.46 mmol)
of NEt3. The reaction mixture was stirred for 16 h at
135–140°С and poured in a Petri dish. On evaporation of
the solvent the residue was subjected to column chroma-
tography on silica gel (eluent chloroform) to isolate 56 mg
(60%) of compound XX, conversion of triflate 66%.
(E)-6-(Methoxycarbonyl)-7-[2-(pyridine-2-yl)
vinyl]-2Н-chromen-2-one (ХХ). a. To solution of
300 mg (0.93 mmol) of peurutenicin triflate (III) in
5 ml of DMF under an argon atmosphere was added
at stirring 194.4 mg (1.86 mmol) of 2-vinylpyridine
(XVIII), 4 mg (2 mol%) of Pd(OAc)2, 23 mg (8 mol%)
of (о-tol)3P, and 0.128 ml (0.93 mmol) of triethylamine.
The reaction mixture was stirred for 7 h at 115°С and
poured in a Petri dish. On evaporation of the solvent the
residue was subjected to column chromatography on
silica gel (eluent chloroform), trace amount of the reaction
product was isolated insufficient for further analysis, and
268 mg of the initial compound.
f. To a solution of 150 mg (0.46 mmol) of peurutenicin
triflate (III) in 3 ml of DMF under an argon atmosphere
was added at stirring in succession 97.2 mg (0.93 mmol)
of 2-vinylpyridine (XVIII), 4 mg (4 mol%) of Pd(OAc)2,
22 mg (8 mol%) of BINAP, and 0.064 ml (0.46 mmol)
of NEt3. The reaction mixture was stirred for 16 h at
135–140°С (TLC monitoring) and poured in a Petri dish.
On evaporation of the solvent the residue was subjected to
column chromatography on silica gel (eluent chloroform),
and after the recrystallization from ether we obtained
106 mg (75%) of compound XX, conversion of triflate
100%, mp 202–204°С (from ethanol). IR spectrum,
cm–1: 3050, 3018, 2852, 1718, 1612, 1585, 1564, 1547,
1500, 1468, 1430, 1380, 1286, 1213, 1182, 1147, 1111,
1072, 991, 966, 910, 845, 825, 789, 762, 740, 700. UV
spectrum (EtOH), λmax, nm (log ε): 200 (4.31), 219 (4.09),
246 (4.21), 333 (4.16). 1Н NMR spectrum, δ, ppm: 3.95 s
(3H, OСH3), 6.43 d (1Н, Н3, J 9.6 Hz), 7.18 d (1Н, Нb,
J 15.8 Hz), 7.21 s (1Н, Н8), 7.28 m (1Н, Н4'), 7.47 d.d
(1Н, Н6', J 7.2, 1.6 Hz), 7.69 m (1Н, Н5'), 7.72 d (1Н, Н4,
J 9.6 Hz), 8.12 s (1Н, Н5), 8.42 d (1Н, Нa, J 15.8 Hz),
8.64 d (1Н, Н3'). 13С NMR spectrum, δ, ppm: 52.06 q
(OСH3), 108.07 d (C8), 112.02 d (С3), 113.34 s (С4a),
119.26 d (C4'), 121.11 d (C6'), 123.08 s (C6), 127.03 d
(C5), 129.27 d (Cb), 136.30 d (C5'), 137.21 d (Cа),138.09 s
(C7), 144.15 d (C4), 149.16 d (C3'), 155.86 s (C1'),161.52 s
(C2), 163.37 s (C8а), 165.87 s (C=O). Found, %: C 67.76;
H 4.59; N 4.78. С18Н13NO4 + 1/3DMF. Calculated, %: С
70.35; H 4.26; N 4.56 (without DMF); С 67.05; H 4.40;
N 5.14 (with DMF).
b. To a solution of 150 mg (0.46 mmol) of peurutenicin
triflate (III) in 3 ml of DMF under an argon atmosphere
was added at stirring in succession 97.2 mg (0.93 mmol)
of 2-vinylpyridine (XVIII), 2 mg (2 mol%) of Pd(OAc)2,
11 mg (8 mol%) of (о-tol)3P, and 0.064 ml (0.46 mmol)
of NEt3. The reaction mixture was stirred for 8 h at
135–140°С and poured in a Petri dish. On evapora-
tion of the solvent the residue was subjected to column
chromatography on silica gel (eluent chloroform). Yield
10 mg (9%) of the reaction product and 100 mg of the
initial compound.
c. To a solution of 150 mg (0.46 mmol) of peurutenicin
triflate (III) in 3 ml of DMF under an argon atmo-
sphere was added at stirring 97.2 mg (0.93 mmol) of
2-vinylpyridine (XVIII), 2 mg (2 mol%) of Pd(OAc)2,
11 mg (8 mol%) of (о-tol)3P, and 0.064 ml (0.46 mmol)
of triethylamine. The reaction mixture was stirred for 10
h at 135–140°С and poured in a Petri dish. On evapora-
tion of the solvent the residue was subjected to column
chromatography on silica gel (eluent chloroform) the
fraction with the reaction product was collected, and
after the recrystallization from ether we isolated 30 mg
(47%) of compound XX, conversion of triflate III 80%.
d. To a solution of 150 mg (0.46 mmol) of peurutenicin
triflate (III) in 3 ml of DMF under an argon atmosphere
was added at stirring in succession 97.2 mg (0.93 mmol)
of 2-vinylpyridine (XVIII), 4 mg (4 mol%) of Pd(OAc)2,
11 mg (8 mol%) of (о-tol)3P, and 0.064 ml (0.46 mmol)
(E)-6-(Methoxycarbonyl)-7-[2-(6-methylpyridin-
3-yl)vinyl]-2Н-chromen-2-one (ХХI). To a solution
of 150 mg (0.46 mmol) of peurutenicin triflate (III) in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

STUDY OF PLANT COUMARINS: X
1101
8.05 d (1Н, Нa, J 15.9 Hz), 8.11 s (1Н, Н5), 8.25 d (1Н,
Н5', J 7.5 Hz), 8.37 d (1Н, Н6', J 7.5 Hz), 8.68 s (1Н, Н3').
13С NMR spectrum, δ, ppm: 52.16 q (OСH3), 109.38 d
(C8), 112.15 d (С3), 113.04 s (С4a), 124.37 s (C6), 126.14 d
(Cb), 130.45 d (C5), 136.35 d (Cа),137.60 s (C7), 139.24 d
(C5'), 140.75 d (C3'), 141.76 d (C6'),144.25 d (C4), 150.46 s
(C2'), 161.29 s (C2), 163.68 s (C8а), 167.21 s (C=O). Found,
%: C 66.15; H 4.05; N 9.03. С17Н12N2O4. Calculated, %:
С 66.23; H 3.92; N 9.09.
3 ml of DMF under an argon atmosphere was added at
stirring in succession 110 mg (0.93 mmol) of 5-vinyl-
2-methylpyridine (XIX), 4 mg (4 mol%) of Pd(OAc)2,
22 mg (8 mol%) of BINAP, and 0.064 ml (0.46 mmol) of
triethylamine. The reaction mixture was stirred for 16 h at
135–140°С (TLC monitoring) and poured in a Petri dish.
On evaporation of the solvent the residue was subjected to
column chromatography on silica gel (eluent chloroform),
and after the recrystallization from ether we obtained
64 mg (43%) of compound XXI, triflate conversion
100%, mp 231–232°С (from ether). IR spectrum, cm–1:
3086, 3008, 2924, 2850, 2717, 1755, 1714, 1616, 1600,
1551, 1491, 1441, 1423, 1383, 1292, 1217, 1178, 1147,
1109, 1070, 1030, 955, 912, 837, 785, 769, 729, 629. UV
spectrum (EtOH), λmax, nm (log ε): 201 (4.30), 246 (4.28),
337 (4.23). 1Н NMR spectrum, δ, ppm: 2.58 s (3Н, СH3
at C3'), 3.95 s (3H, OСH3), 6.44 d (1Н, Н3, J 9.6 Hz),
7.04 d (1Н, Нb, J 16.6 Hz), 7.18 d (1Н, Н5', J 7.6 Hz),
7.61 s (1Н, Н8), 7.70 d (1Н, Н4, J 9.6 Hz), 7.81 d.d (1Н,
Н4', J 7.6, 1.8 Hz), 8.08 d (1Н, Нa, J 16.6 Hz), 8.14 s (1Н,
Н5), 8.63 d (1Н, Н2', J 1.8 Hz). 13С NMR spectrum, δ,
ppm: 23.55 q (OСH3), 52.18 q (OСH3), 108.56 d (C8),
112.54 d (С3), 113.39 s (С4a), 119.93 d (C5'), 122.21 s (C6),
123.91 d (Cb), 125.34 d (C5), 130.44 d (C1'), 130.82 d (C4'),
131.87 d (Cа),137.56 s (C7), 142.96 d (C2'), 144.15 d (C4),
157.18 s (C6'), 160.59 s (C2), 163.15 s (C8а), 167.13 s
(C=O). Found, %: С 70.67; Н 4.84; N 4.64. С19Н15NO4.
Calculated, %: С 71.02; H 4.71; N 4.36.
(E)-6-(Methoxycarbonyl)-7-[2-(1H-1,2,4-triazol-
1-yl)vinyl]-2Н-chromen-2-one (XXV). To a solution
of 100 mg (0.3 mmol) of peurutenicin triflate (III) in
3 ml of DMF under an argon atmosphere was added at
stirring in succession 60 mg (0.6 mmol) of 1-vinyl-1H-
1,2,4-triazole (XXIII), 2.7 mg (4 mol%) of Pd(OAc)2,
15 mg (8 mol%) of BINAP, and 0.042 ml (0.3 mmol) of
triethylamine. The reaction mixture was stirred for 16 h at
135–140°С (TLC monitoring) and poured in a Petri dish.
On evaporation of the solvent the residue was subjected to
column chromatography on silica gel (eluent chloroform),
and after the recrystallization from ether we obtained
40 mg (45%) of compound XXV, mp 239–240°С (from
ether). IR spectrum, cm–1: 2922, 2852, 1721, 1680, 1660,
1624, 1600, 1558, 1507, 1500, 1438, 1283, 1214, 1149,
1111, 1048, 1000, 961, 908, 828, 750, 674. UV spectrum
(EtOH), λmax, nm (log ε): 200 (4.72), 242 (4.30), 273
1
(3.84), 295 (3.92), 319 (4.00). Н NMR spectrum, δ,
ppm: 3.87 s (3H, OСH3), 6.40 d (1Н, Н3, J 9.8 Hz),
7.50 d (1Н, Нb, J 15.8 Hz), 7.46 s (1Н, Н8), 7.70 d (1Н,
Н4, J 9.8Hz), 8.08 d (1Н, Нa, J 15.8 Hz), 7.98 s (1Н, Н5'),
8.09 s (1Н, Н5), 8.43 br.s (1Н, Н3'). 13С NMR spectrum,
δ, ppm: 52.19 q (OСH3), 107.40 d (C8), 110.56 s (С4a),
113.36 d (С3), 118.27 d (Cb), 121.07 d (C5), 122.36 d (Cа),
128.21 s (C6), 137.11 s (C7), 144.46 d (C4), 145.63 d (C5'),
154.28 s (C3'), 161.06 s (C2), 166.22 s (C8а), 167.26 s
(C=O). Found, %: C 60.88; H 3.52; N 14.05. С15Н11N3O4.
Calculated, %: С 60.61; H 3.73; N 14.14.
(E)-6-(Methoxycarbonyl)-7-[2-(pyrazin-2-yl)-
vinyl]-2Н-chromen-2-one (ХХIV). To a solution of
100 mg (0.3 mmol) of peurutenicin triflate (III) in 3 ml of
DMF under an argon atmosphere was added at stirring in
succession 63 mg (0.6 mmol) of 2-vinylpyrazine (XXII),
2.7 mg (4 mol%) of Pd(OAc)2, 15 mg (8 mol%) of BINAP,
and 0.042 ml (0.3 mmol) of NEt3. The reaction mixture
was stirred for 16 h at 135–140°С (TLC monitoring)
and poured in a Petri dish. On evaporation of the solvent
the residue was subjected to column chromatography on
silica gel (eluent chloroform), and after the recrystalliza-
tion from ether we obtained 51 mg (56%) of compound
XXIV, mp 200–201°С (from ether). IR spectrum, cm–1:
3058, 2955, 2922, 2851, 1718, 1680, 1620, 1548, 1500,
1488, 1405, 1379, 1285, 1212, 1184, 1149, 1106, 1070,
1031, 1017, 962, 913, 866, 826, 805, 785, 751, 720, 699.
UV spectrum (EtOH), λmax, nm (log ε): 201 (4.29), 230
(4.16), 247 (4.33), 335 (4.23). 1Н NMR spectrum, δ, ppm:
3.89 s (3H, OСH3), 6.42 d (1Н, Н3, J 9.6 Hz), 7.08 d (1Н,
Нb, J 15.9 Hz), 7.59 s (1Н, Н8), 7.69 d (1Н, Н4, J 9.6 Hz),
(E)-6-(Methoxycarbonyl)-7-styryl-2Н-chromen-
2-one (XXVII). To a solution of 150 mg (0.46 mmol)
of peurutenicin triflate (III) in 3 ml of DMF under an
argon atmosphere was added at stirring in succession
97 mg (0.93 mmol) of styrene (XXVI), 4 mg (4 mol%)
of Pd(OAc)2, 22 mg (8 mol%) of BINAP, and 0.064 ml
(0.46 mmol) of triethylamine. The reaction mixture was
stirred for 16 h at 135–140°С (TLC monitoring) and
poured in a Petri dish. On evaporation of the solvent the
residue was subjected to column chromatography on
silica gel (eluent chloroform), and after the recrystalliza-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

MAKHNEVA et al.
1102
Glowniak, K., Phytochem., 2005, vol. 66, p. 707; Chinou,
I., Widelski, J., Fokialakis, N., Magiatis, P., Glowniak, K.,
Fitoterapia, 2007, vol. 78, p. 448.
tion from ether we obtained 112 mg (79%) of compound
ХХVII, mp 240–242°С (from ether). IR spectrum, cm–1:
3059, 3026, 2966, 2927, 2856, 1734, 1678, 1624, 1600,
1580, 1487, 1450, 1389, 1354, 1281,1203, 1165, 1140,
1060, 1036, 900, 820, 806, 756, 717, 696. UV spectrum
(EtOH), λmax, nm (log ε): 203 (4.50), 230 (4.08), 250
3. Ahluwalia, V.K. and Prakash, C., Ind. J. Chem., 1977,
no. 15B, p. 423.
4. Osadchii, S.A., Shul’ts, E.E., Shakirov, M.M., and Tols-
tikov, G.A., Izv. Akad. Nauk, Ser. Khim., 2006, p. 362.
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olvi, M.N., Sapkal, S., Dharbhamulla, S., and Maddi, V.S.,
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Hartmann, R.W., and Carotti, A., J. Med. Chem., 2004,
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P.-A., Altomare, C., Carotti, A., and Testa, B., J. Med.
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vol. 49, p. 4912; Chimenti, F., Secci, D., Bolasco, A.,
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1
(3.71), 271 (3.52), 279 (3.48), 335 (3.54). Н NMR
spectrum, δ, ppm: 3.80 s (3H, OСH3), 6.19 d (1Н, Н3,
J 9.6 Hz), 6.74 d (1Н, Нb, J 14.8 Hz), 6.88 d (1Н, Нa,
J 14.8 Hz), 7.16 m (2Н, Н2',6'), 7.23 m (3Н, Н3',4',5'),
7.41 s (1Н, Н8), 7.77 d (1Н, Н4, J 9.6 Hz), 8.36 s (1Н,
Н5). 13С NMR spectrum, δ, ppm: 52.33 q (OСH3),
106.02 d (C8), 112.96 d (С3), 113.08 s (С4a), 124.31 d
(Cb), 125.34 d (C2',6'), 125.80 s (C6), 125.66 d (C4'),
128.58 d (C3',5'), 129.34 d (C5), 130.14 d (Cа), 137.10 d
(C1'),137.41 s (C7), 144.45 d (C4), 159.70 s (C2), 163.80 s
(C8а), 168.05 s (C=O). Found, %: C 74.61; H 4.82.
С19Н14O4·Н2О. Calculated, %: С 74.50; H 4.61.
ACKNOWLEDGMENTS
8. Starčević, Š., Brožič, P., Turk, S., Cesar, J., Rižner, T.L.,
and Gobec, S., J. Med. Chem., 2011, vol. 54, p. 248.
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Adamopoulos, S.G., J. Heterocycl. Chem., 1998, vol. 35,
p. 91.
10. Cacchi, S., Fabrizi, G., Lamba, D., Marinelli, F., and Pa-
risi, L.M., Synthesis, 2003, 728; Cacchi, S., Fabrizi, G., and
Parisi, L.M., Synthesis, 2004, p. 1889.
The study was carried out under the financial sup-
port of the Russian Foundation for Basic Research
(grant no. 11-03-00242-а) and of the Program of the
President of the Russian Federation for the support of
the leading scientific schools (grant NSh-3986.2012.3).
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