Five-membered 2,3-dioxo heterocycles: LVI. Reaction of 3-aroyl-1H- pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with acyclic enamino ketones

Article abstract of DOI:10.1134/S1070428008040192

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with 4-arylaminopent-3-en-2-ones and 3-amino-1,3-diphenylprop-2-en-1-ones to give substituted 4-aroyl-3-hydroxy-1-(o-hydroxyphenyl)-1,7-diazaspiro[4.4]nona-3,8- diene-2,6-diones.

Full text of DOI:10.1134/S1070428008040192

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 4, pp. 582–586. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.L. Racheva, M.A. Belova, A.N. Maslivets, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 4, pp. 587–591.
Five-Membered 2,3-Dioxo Heterocycles: LVI.* Reaction
of 3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones
with Acyclic Enamino Ketones
N. L. Racheva, M. A. Belova, and A. N. Maslivets
Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received May 16, 2006
Abstract—3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with 4-arylaminopent-3-en-2-ones
and 3-amino-1,3-diphenylprop-2-en-1-ones to give substituted 4-aroyl-3-hydroxy-1-(o-hydroxyphenyl)-1,7-di-
azaspiro[4.4]nona-3,8-diene-2,6-diones.
DOI: 10.1134/S1070428008040192
Recyclizations and heterocyclizations of 4-acyl-1H-
pyrrole-2,3-diones, including those fused to a nitrogen-
containing heteroring at the a side, by the action of
difunctional nucleophiles are widely used as an acces-
sible method for building up various fused heterocyclic
systems [2, 3]. We previously showed that 4-acyl-1H-
pyrrole-2,3-diones fused to 1,4-benzoxazine system,
namely 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-
1,2,4-triones Ia–Ic [4], react with cyclic enamino
ketones (3-amino-5,5-dimethylcyclohex-2-en-1-ones,
both N-substituted and N-unsubstituted) as with
1,3-C,N-binucleophiles. The reaction involves succes-
sive attack by the β-CH and NH groups of enamino
ketone on the C3a and C4 carbon atoms, respectively,
Scheme 1.
R2
HN
O
N
O
O
R1
O
N
O
R1
R1
R2
O
+
COR1
O
N
Ar
·
·
·
H
COAr
O
O
OH
Ia–Ic
IIa–IIf
R2
N
O
R1
N
COR1
HO
O
COAr
OH
IIIa–IIIr
I, Ar = Ph (a), 4-MeOC6H4 (b), 4-BrC6H4 (c); II, R1 = Me, R2 = Ph (a), 4-MeOC6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d); R1 = Ph,
R2 = PhCH2 (e), 4-EtOC6H4 (f); III, R1 = Me (a–l), Ph (m–r); Ar = R2 = Ph (a); Ar = 4-MeOC6H4, R2 = Ph (b); Ar = 4-BrC6H4, R2 =
Ph (c); Ar = Ph, R2 = 4-MeOC6H4 (d); Ar = R2 = 4-MeOC6H4 (e); Ar = 4-BrC6H4, R2 = 4-MeOC6H4 (f); Ar = Ph, R2 = 4-ClC6H4 (g);
Ar = 4-MeOC6H4, R2 = 4-ClC6H4 (h); Ar = 4-BrC6H4Br, R2 = 4-ClC6H4 (i); Ar = Ph, R2 = 4-BrC6H4 (j); Ar = 4-MeOC6H4,
R2 = 4-BrC6H4 (k); Ar = R2 = 4-BrC6H4 (l); Ar = Ph, R2 = PhCH2 (m); Ar = 4-MeOC6H4, R2 = PhCH2 (n); Ar = 4-BrC6H4, R2 =
PhCH2 (o); Ar = Ph, R2 = 4-EtOC6H4 (p); Ar = 4-MeOC6H4, R2 = 4-EtOC6H4 (q); Ar = 4-BrC6H4, R2 = 4-EtOC6H4 (r).
* For communication LV, see [1].
582

FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LVI.
583
of pyrrolobenzoxazinetrione and is accompanied by
cleavage of the oxazine ring at the C4–O5 bond to give
3′-aroyl-4′-hydroxy-1′-(o-hydroxyphenyl)-6,6-di-
methyl-6,7-dihydrospiro[indole-3,2′-pyrrole]-2,4,5′-
(1H,1′H,5H)-triones [5] whose structure was proved by
X-ray analysis.
singlets from the 8-methyl group and 9-acetyl group
at δ 2.04–2.08 and 2.17–2.21 ppm, respectively (IIIa–
IIIl), a doublet of doublets from the diastereotopic
benzylic protons at δ 4.39–4.80 ppm (IIIm–IIIo),
a singlet from the phenolic hydroxy proton at δ 9.94–
10.20 (IIIa–IIIl) or 9.53–9.76 ppm (IIIm–IIIr), and
a broadened singlet from the enolic hydroxy proton at
δ 12.00–12.70 ppm.
In continuation of our studies on reactions of het-
areno[a]pyrrole-2,3-diones with difunctional nucleo-
philes, in the present work we examined reactions of
3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-tri-
ones Ia–Ic with acyclic enamino ketones, 4-arylamino-
pent-3-en-2-ones IIa–IId and N-substituted 3-amino-
1,3-diphenylprop-2-en-1-ones IIe and IIf. Unlike
cyclic analogs, acyclic enamino ketones IIa–IIf exist
as Z isomers with intramolecular hydrogen bond
formed by the NH proton and ketone carbonyl oxygen
atom, and the β-CH and NH groups are oriented at
different sides with respect to the double C=C bond,
which makes compounds II difficult to react as binu-
cleophiles. Cyclic enamino ketones exist as E isomers
where the β-CH and NH groups are arranged at the
same side of the double bond, and such arrangement
favors their behavior as binucleophiles.
Presumably, in the first step activated β-CH group
in acyclic enamino ketone II adds at the carbon atom
in the 3a-position of pyrrolobenzoxazinetrione I, as
in reactions of the latter with common nucleophiles
[2–4]. Next follows isomerization of the enamino
fragment from Z configuration to E and pyrrole ring
closure as a result of intramolecular attack by the
amino group on the lactone carbonyl carbon atom (C4)
in the oxazine ring of I, which is accompanied by
cleavage of the C4–O5 bond. The described reaction
may be regarded as a fairly rare example of regioselec-
tive synthesis of difficultly accessible spiro-fused
bipyrrole heterocyclic system with various substituents
in several positions of both pyrrole rings.
EXPERIMENTAL
By heating equimolar amounts of pyrrolobenzoxa-
zinetriones Ia–Ic and enamino ketones IIa–IIf in
boiling anhydrous benzene for 3–7 min (until dark
violet color typical of initial compounds I disappeared)
we obtained in high yields substituted 4-aroyl-3-hy-
droxy-1-(o-hydroxyphenyl)-1,7-diazaspiro[4.4]nona-
3,8-diene-2,6-diones IIIa–IIIr** (Scheme 1). Com-
pounds IIIa–IIIr were isolated as colorless or light
yellow crystalline substances melting at high tempera-
ture with decomposition; they are readily soluble in
DMF and DMSO, poorly soluble in most other organic
solvents, and insoluble in saturated hydrocarbons and
water. Compounds IIIa–IIIr showed a positive test
(cherry color) for enolic and phenolic hydroxy groups
with an alcoholic solution of iron(III) chloride.
The IR spectra were recorded on a UR-20 spec-
trometer from samples dispersed in mineral oil. The
1H and 13C NMR spectra were measured on a Bruker
1
AM-400 instrument (400 MHz for H) from solutions
in DMSO-d6 using tetramethylsilane as internal refer-
ence. The purity of the products was checked by thin-
layer chromatography on Silufol plates using ethyl
acetate or ethyl acetate–benzene (1:5) as eluent; spots
were detected by treatment with iodine vapor.
9-Acetyl-4-benzoyl-3-hydroxy-1-(2-hydroxy-
phenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-
3,8-diene-2,6-dione (IIIa). A solution of 1.0 mmol of
compound Ia and 1.0 mmol of enamine IIa in 10 ml of
anhydrous benzene was heated for 3 min under reflux.
The mixture was cooled, and the precipitate was
filtered off. Yield 88%, mp 198–199°C (from EtOAc).
IR spectrum, ν, cm–1: 3050 br (OH), 1765 (C6=O),
1705 (C2=O), 1640 and 1626 (4-C=O, 9-C=O).
1H NMR spectrum, δ, ppm: 2.07 s (3H, Me), 2.21 s
(3H, MeCO), 6.89–7.85 m (14H, Harom), 10.00 s (1H,
2′-OH), 12.70 br.s (1H, 3-OH). Found, %: C 70.40;
H 4.67; N 5.62. C29H22N2O6. Calculated, %: C 70.44;
H 4.48; N 5.67.
The IR spectra of spirobipyrroles IIIa–IIIr con-
tained absorption bands due to stretching vibrations of
the OH groups (a broad band in the region 3040–
3170 cm–1), lactam carbonyl groups (one or two peaks
at 1700–1769 cm–1), and acetyl and aroyl carbonyl
groups (two peaks at 1620–1688 cm–1 in the spectra of
IIIa–IIIl and at 1620–1682 cm–1 in the spectra of
IIIm–IIIr). Compounds IIIa–IIIr showed in the
1H NMR spectra (DMSO-d6) signals from protons in
the aromatic rings and substituents attached thereto,
Compounds IIIb–IIIr were synthesized in a similar
** For preliminary communication, see [6].
way.
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RACHEVA et al.
584
1
and 1626 (4-C=O, 9-C=O). H NMR spectrum, δ,
ppm: 2.04 s (3H, Me), 2.18 s (3H, MeCO), 3.81 s (3H,
OMe), 6.82–7.75 m (12H, Harom), 9.99 s (1H, 2′-OH),
12.50 br.s (1H, 3-OH). Found, %: C 59.78; H 3.93;
Br 13.41; N 4.55. C30H23BrN2O7. Calculated, %:
C 59.71; H 3.84; Br 13.24; N 4.64.
9-Acetyl-3-hydroxy-1-(2-hydroxyphenyl)-4-
(4-methoxybenzoyl)-8-methyl-7-phenyl-1,7-diaza-
spiro[4.4]nona-3,8-diene-2,6-dione (IIIb). Yield
97%, mp 209–212°C (from EtOAc). IR spectrum, ν,
cm–1: 3160 br (OH), 1754 (C6=O), 1703 (C2=O), 1667
1
and 1628 (4-C=O, 9-C=O). H NMR spectrum, δ,
ppm: 2.05 s (3H, Me), 2.18 s (3H, MeCO), 3.86 s (3H,
OMe), 6.82–7.87 m (13H, Harom), 9.98 s (1H, 2′-OH),
12.53 br.s (1H, 3-OH). Found, %: C 68.59; H 4.71;
N 5.36. C30H24N2O7. Calculated, %: C 68.70; H 4.61;
N 5.34.
9-Acetyl-4-benzoyl-7-(4-chlorophenyl)-3-hy-
droxy-1-(2-hydroxyphenyl)-8-methyl-1,7-diaza-
spiro[4.4]nona-3,8-diene-2,6-dione (IIIg). Yield
88%, mp 200–203°C (from benzene). IR spectrum, ν,
cm–1: 3170 br (OH), 1748 (C6=O), 1711 (C2=O), 1668
1
9-Acetyl-4-(4-bromobenzoyl)-3-hydroxy-1-(2-hy-
droxyphenyl)-8-methyl-7-phenyl-1,7-diazaspiro-
[4.4]nona-3,8-diene-2,6-dione (IIIc). Yield 87%,
mp 210–211°C (from EtOAc). IR spectrum, ν, cm–1:
3170 br (OH), 1753 (C6=O), 1703 (C2=O), 1666 and
and 1627 (4-C=O, 9-C=O). H NMR spectrum, δ,
ppm: 2.07 s (3H, Me), 2.20 s (3H, MeCO), 6.86–
7.92 m (13H, Harom), 10.20 s (1H, 2′-OH), 12.40 br.s
(1H, 3-OH). Found, %: C 65.69; H 4.21; Cl 6.65;
N 5.39. C29H21ClN2O6. Calculated, %: C 65.85;
H 4.00; Cl 6.70; N 5.30.
1
1631 (4-C=O, 9-C=O). H NMR spectrum, δ, ppm:
2.07 s (3H, Me), 2.20 s (3H, MeCO), 6.85–7.76 m
(13H, Harom), 10.02 s (1H, 2′-OH), 12.40 br.s (1H,
3-OH). Found, %: C 60.87; H 3.63; Br 14.07; N 5.01.
C29H21BrN2O6. Calculated, %: C 60.75; H 3.69;
Br 13.94; N 4.89.
9-Acetyl-7-(4-chlorophenyl)-3-hydroxy-1-(2-hy-
droxyphenyl)-4-(4-methoxybenzoyl)-8-methyl-1,7-
diazaspiro[4.4]nona-3,8-diene-2,6-dione (IIIh).
Yield 87%, mp 216–217°C (from benzene). IR spec-
trum, ν, cm–1: 3160 br (OH), 1744 (C6=O), 1703
9-Acetyl-4-benzoyl-3-hydroxy-1-(2-hydroxy-
phenyl)-7-(4-methoxyphenyl)-8-methyl-1,7-diaza-
spiro[4.4]nona-3,8-diene-2,6-dione (IIId). Yield
85%, mp 228–230°C (from EtOAc). IR spectrum, ν,
cm–1: 3100 br (OH), 1764 (C6=O), 1713 (C2=O), 1665,
1
(C2=O), 1669 and 1626 (4-C=O, 9-C=O). H NMR
spectrum, δ, ppm: 2.07 s (3H, Me), 2.20 s (3H,
MeCO), 3.86 s (3H, OMe), 6.86–7.87 m (12H, Harom),
10.00 s (1H, 2′-OH), 12.50 br.s (1H, 3-OH). Found, %:
C 64.58; H 4.09; Cl 6.39; N 4.92. C30H23ClN2O7. Cal-
culated, %: C 64.46; H 4.15; Cl 6.34; N 5.01.
1
1634 (4-C=O, 9-C=O). H NMR spectrum, δ, ppm:
2.05 s (3H, Me), 2.19 s (3H, MeCO), 3.81 s (3H,
OMe), 6.83–8.03 m (13H, Harom), 9.99 s (1H, 2′-OH),
12.70 br.s (1H, 3-OH). Found, %: C 68.77; H 4.54;
N 5.27. C30H24N2O7. Calculated, %: C 68.70; H 4.61;
N 5.34.
9-Acetyl-4-(4-bromobenzoyl)-7-(4-chlorophen-
yl)-3-hydroxy-1-(2-hydroxyphenyl)-8-methyl-1,7-
diazaspiro[4.4]nona-3,8-diene-2,6-dione (IIIi). Yield
89%, mp 199–201°C (from BuOAc). IR spectrum, ν,
cm–1: 3150 br (OH), 1759 (C6=O), 1708 (C2=O), 1673
9-Acetyl-3-hydroxy-1-(2-hydroxyphenyl)-4-(4-
methoxybenzoyl)-7-(4-methoxyphenyl)-8-methyl-
1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione (IIIe).
Yield 87%, mp 220–222°C (from BuOAc). IR spec-
trum, ν, cm–1: 3150 br (OH), 1732 (C6=O, C2=O), 1688
1
and 1638 (4-C=O, 9-C=O). H NMR spectrum, δ,
ppm: 2.08 s (3H, Me), 2.18 s (3H, MeCO), 6.82–
7.75 m (12H, Harom), 10.00 s (1H, 2′-OH), 12.50 br.s
(1H, 3-OH). Found, %: C 57.33; H 3.30; Br 13.24;
Cl 5.79; N 4.57. C29H20BrClN2O6. Calculated, %:
C 57.30; H 3.32; Br 13.15; Cl 5.83; N 4.61.
1
and 1638 (4-C=O, 9-C=O). H NMR spectrum, δ,
ppm: 2.04 s (3H, Me), 2.17 s (3H, MeCO), 3.81 s (3H,
OMe), 3.87 s (3H, OMe), 6.82–7.87 m (12H, C6H4),
9.98 s (1H, 2′-OH), 12.50 br.s (1H, 3-OH). Found, %:
C 67.84; H 4.82; N 5.02. S31N26N2O8. Calculated, %:
C 67.74; H 4.73; N 5.05.
9-Acetyl-4-benzoyl-7-(4-bromophenyl)-3-hy-
droxy-1-(2-hydroxyphenyl)-8-methyl-1,7-diaza-
spiro[4.4]nona-3,8-diene-2,6-dione (IIIj). Yield 90%,
mp 203–204°C (from benzene). IR spectrum, ν, cm–1:
3170 br (OH), 1748 (C6=O), 1711 (C2=O), 1672 and
9-Acetyl-4-(4-bromobenzoyl)-3-hydroxy-1-(2-hy-
droxyphenyl)-7-(4-methoxyphenyl)-8-methyl-1,7-di-
azaspiro[4.4]nona-3,8-diene-2,6-dione (IIIf). Yield
86%, mp 209–210°C (from BuOAc). IR spectrum, ν,
cm–1: 3110 br (OH), 1765 (C6=O), 1704 (C2=O), 1663
1
1628 (4-C=O, 9-C=O). H NMR spectrum, δ, ppm:
2.07 s (3H, Me), 2.21 s (3H, MeCO), 6.80–7.93 m
(13H, Harom), 9.94 s (1H, 2′-OH), 12.40 br.s (1H,
3-OH). Found, %: C 60.68; H 3.77; Br 13.78; N 5.02.
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FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LVI.
585
C29H21BrN2O6. Calculated, %: C 60.75; H 3.69;
Br 13.94; N 4.89.
cm–1: 3050 br (OH), 1730 (C6=O, C2=O), 1677 and
1636 (4-C=O, 9-C=O). H NMR spectrum, δ, ppm:
1
4.39 d.d and 4.79 d.d (1H each, CH2Ph, J = 16.3 Hz),
6.62–7.81 m (23H, Harom), 9.66 s (1H, 2′-OH),
12.60 br.s (1H, 3-OH). Found, %: C 67.61; H 3.79;
Br 11.25; N 3.86. C40H27BrN2O6. Calculated, %:
C 67.52; H 3.82; Br 11.23; N 3.94.
9-Acetyl-7-(4-bromophenyl)-3-hydroxy-1-(2-hy-
droxyphenyl)-4-(4-methoxybenzoyl)-8-methyl-1,7-
diazaspiro[4.4]nona-3,8-diene-2,6-dione (IIIk).
Yield 89%, mp 220–221°C (from benzene). IR spec-
trum, ν, cm–1: 3130 br (OH), 1733 (C6=O), 1713
1
(C2=O), 1661 and 1620 (4-C=O, 9-C=O). H NMR
4,9-Dibenzoyl-7-(4-ethoxyphenyl)-3-hydroxy-1-
(2-hydroxyphenyl)-8-phenyl-1,7-diazaspiro[4.4]-
nona-3,8-diene-2,6-dione (IIIp). Yield 92%, mp 269–
270°C (from EtOAc). IR spectrum, ν, cm–1: 3150 br
(OH), 1769 (C6=O), 1728 (C2=O), 1668 and 1634
spectrum, δ, ppm: 2.07 s (3H, Me), 2.18 s (3H,
MeCO), 3.86 s (3H, OMe), 6.81–7.87 m (12H, Harom),
10.00 s (1H, 2′-OH), 12.00 br.s (1H, 3-OH). Found, %:
C 59.62; H 3.78; Br 13.30; N 4.57. C30H23BrN2O7.
Calculated, %: C 59.71; H 3.84; Br 13.24; N 4.64.
1
(4-C=O, 9-C=O). H NMR spectrum, δ, ppm: 1.27 t
(3H, CH3, J = 6.9 Hz), 4.03 q (2H, OCH2, J = 7.0 Hz),
6.61–7.92 m (23H, Harom), 9.76 s (1H, 2′-OH),
12.40 br.s (1H, 3-OH). Found, %: C 74.26; H 4.61;
N 4.29. C41H30N2O7. Calculated, %: C 74.31; H 4.56;
N 4.23.
9-Acetyl-4-(4-bromobenzoyl)-7-(4-bromophen-
yl)-3-hydroxy-1-(2-hydroxyphenyl)-8-methyl-1,7-
diazaspiro[4.4]nona-3,8-diene-2,6-dione (IIIl). Yield
88%, mp 225–226°C (from benzene). IR spectrum, ν,
cm–1: 3070 br (OH), 1736 (C6=O), 1719 (C2=O), 1661
1
and 1626 (4-C=O, 9-C=O). H NMR spectrum, δ,
9-Benzoyl-7-(4-ethoxyphenyl)-3-hydroxy-1-(2-
hydroxyphenyl)-4-(4-methoxybenzoyl)-8-phenyl-
1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione (IIIq).
Yield 90%, mp 258–259°C (from EtOAc). IR spec-
trum, ν, cm–1: 3140 br (OH), 1726 (C6=O), 1700
ppm: 2.08 s (3H, Me), 2.18 s (3H, MeCO), 6.81–
7.79 m (12H, Harom), 10.00 s (1H, 2′-OH), 12.40 br.s
(1H, 3-OH). Found, %: C 53.37; H 3.11; Br 24.58;
N 4.23. C29H20Br2N2O6. Calculated, %: C 53.40;
H 3.09; Br 24.50; N 4.29.
1
(C2=O), 1665 and 1630 (4-C=O, 9-C=O). H NMR
4,9-Dibenzoyl-7-benzyl-3-hydroxy-1-(2-hydroxy-
phenyl)-8-phenyl-1,7-diazaspiro[4.4]nona-3,8-di-
ene-2,6-dione (IIIm). Yield 90%, mp 279–281°C
(from EtOAc). IR spectrum, ν, cm–1: 3040 br (OH),
1727 (C6=O, C2=O), 1682 and 1632 (4-C=O, 9-C=O).
1H NMR spectrum, δ, ppm: 4.39 d.d and 4.80 d.d (1H
each, CH2Ph, J = 16.5 Hz), 6.62–7.89 m (24H, Harom),
9.64 s (1H, 2′-OH), 12.40 br.s (1H, 3-OH). Found, %:
C 75.98; H 4.52; N 4.34. C40H28N2O6. Calculated, %:
C 75.94; H 4.46; N 4.43.
spectrum, δ, ppm: 1.28 t (3H, Me, J = 6.9 Hz), 3.88 s
(3H, OMe), 3.95 q (2H, OCH2, J = 7.1 Hz), 6.59–
7.92 m (22H, Harom), 9.72 s (1H, 2′-OH), 12.20 br.s
(1H, 3-OH). Found, %: C 72.73; H 4.69; N 4.10.
C42H32N2O8. Calculated, %: C 72.82; H 4.66; N 4.04.
9-Benzoyl-4-(4-bromobenzoyl)-7-(4-ethoxy-
phenyl)-3-hydroxy-1-(2-hydroxyphenyl)-8-phenyl-
1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione (IIIr).
Yield 91%, mp 262–263°C (from EtOAc). IR spec-
trum, ν, cm–1: 3150 br (OH), 1736 (C6=O), 1723
1
(C2=O), 1671 and 1620 (4-C=O, 9-C=O). H NMR
9-Benzoyl-7-benzyl-3-hydroxy-1-(2-hydroxy-
phenyl)-4-(4-methoxybenzoyl)-8-phenyl-1,7-diaza-
spiro[4.4]nona-3,8-diene-2,6-dione (IIIn). Yield
89%, mp 272–273°C (from EtOAc). IR spectrum, ν,
cm–1: 3130 br (OH), 1736 (C6=O), 1709 (C2=O), 1681
spectrum, δ, ppm: 1.27 t (3H, Me, J = 6.9 Hz ), 3.95 q
(2H, OCH2, J = 6.9 Hz), 6.60–7.86 m (22H, Harom),
9.76 s (1H, 2′-OH), 12.60 br.s (1H, 3-OH). Found, %:
C 66.37; H 3.99; Br 10.81; N 3.74. C41H29BrN2O7.
Calculated, %: C 66.40; H 3.94; Br 10.77; N 3.78.
1
and 1628 (4-C=O, 9-C=O). H NMR spectrum, δ,
ppm: 3.88 s (3H, OMe), 4.39 d.d and 4.80 d.d (1H
each, CH2Ph, J = 16.5 Hz), 6.66–7.90 m (23H, Harom),
9.53 s (1H, 2′-OH), 12.20 br.s (1H, 3-OH). Found, %:
C 74.37; H 4.63; N 4.14. C41H30N2O7. Calculated, %:
C 74.31; H 4.56; N 4.23.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 07-03-96036).
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