Synthesis and modification of light-sensitive 3-acyl-2-hetarylchromones containing bromomethyl group in the acyl fragment

Article abstract of DOI:10.1007/s11172-012-0242-z

A synthesis of photosensitive 3-acyl-2-hetarylchromones containing bromomethyl group in the 3-aroyl fragment and their further modification by the reactions with N-, S- and O-nucleophiles are described. A dependence of spectral properties from the structu

Full text of DOI:10.1007/s11172-012-0242-z

Russian Chemical Bulletin, International Edition, Vol. 61, No. 9, pp. 1761—1768, September, 2012
1761
Synthesis and modification of lightꢀsensitive 3ꢀacylꢀ2ꢀhetarylchromones
containing bromomethyl group in the acyl fragment
I. S. Semenova, K. S. Levchenko, V. N. Yarovenko, M. M. Krayushkin, V. A. Barachevskii,c
a
b
a
a
O. I. Kobeleva, and T. M. Valovac
c
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
4
7 Leninsky prosp., 119991 Moscow, Russian Federation.
Eꢀmail: yarov@ioc.ac.ru
b"Tekhnomash" Central Research Technological Institute,
4
ul. Ivana Franko, 121108 Moscow, Russian Federation
c
Center of Photochemistry, Russian Academy of Sciences,
a, korp. 1 ul. Novatorov, 119421 Moscow, Russian Federation
7
A synthesis of photosensitive 3ꢀacylꢀ2ꢀhetarylchromones containing bromomethyl group in
the 3ꢀaroyl fragment and their further modification by the reactions with Nꢀ, Sꢀ and
Oꢀnucleophiles are described. A dependence of spectral properties from the structure of comꢀ
pounds was studied.
Key words: chromones, nucleophilic substitution, recording media, fluorescence.
Chromone fragment is a structural part of many natuꢀ
rally occurring compounds exhibiting a wide range of bioꢀ
logical activity.1 Many chromones possess fluorescent
properties and are used as sensors in the studies of microꢀ
scopy of protein, microorganels, and cells.5 Developꢀ
ment of methods for the synthesis of new chromone derivꢀ
atives and their modification is of undoubted practiꢀ
cal interest.
One of the promising directions in development of phoꢀ
tosensitive chromone derivatives consists in the studies of
the influence of substituents on their photochemical propꢀ
erties. In the present work, we continued our investigaꢀ
tions on the influence of structural factors on spectroscopꢀ
ic properties of 3ꢀacylꢀ2ꢀhetarylchromones.
—4
—7
A bromomethyl group is considered as a convenient
fragment for modification of chromones. As it is known,
a bromine atom in bromomethyl group directly bonded to
the aromatic ring is highly reactive, and the corresponding
compounds are readily involved in the reactions with
different nucleophiles, which is used in the synthesis
of various functionally substituted compounds and polyꢀ
meric systems. A possibility of modification of 3ꢀacylꢀ
2ꢀarylchromones under mild conditions allows one to
avoid side reactions frequently taking place upon the acꢀ
tion of bases, including the disintegration of the pyranꢀ
Earlier, we have shown that 3ꢀacylꢀ2ꢀfurylchromone
derivatives were promising components of recording meꢀ
dia for performing single twoꢀphoton bitꢀbyꢀbit record on
multilayer optical disks of superhigh informational capaꢀ
city.8 It is known that 3ꢀacylꢀ2ꢀfurylchromones in the
initial form A do not possess fluorescence, but upon irꢀ
radiation with UV light undergo irreversible photochemiꢀ
,9
cal transformation with the formation of fluorescing
form B,1
0,11
which provides multiple fluorescent reading
1
2—14
of optical information (Scheme 1).
one ring.
Scheme 1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1745—1752, September, 2012.
066ꢀ5285/12/6109ꢀ1761 © 2012 Springer Science+Business Media, Inc.
1

1
762
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Semenova et al.
In order to search for new lightꢀsensitive compounds,
peroxide resulted in the synthesis of bromo derivatives 7a—e
(Scheme 2).
which are of interest as components of multilayer recording
media for the archive storage of optical information, we
accomplished the synthesis of earlier undescribed 3ꢀacylꢀ
ꢀhetarylchromones containing bromomethyl groups in
the acyl fragment. The scheme of chromone synthesis inꢀ
The bromine atom in the compounds obtained is readiꢀ
ly replaced upon the action of Sꢀ, Nꢀ, Oꢀnucleophiles,
which results in the synthesis of the structures 8a—e, 9a—d,
and 10. The reaction conditions and the introduced subꢀ
stituents R are given in Table 1.
2
cluded acylation of 2ꢀhydroxyacetophenone (1) with
4
ꢀmethylbenzoic and 5ꢀmethylthiopheneꢀ2ꢀcarboxilic acyl
The spectral and kinetic studies of photochemiꢀ
cal transformations of the synthesized chromones showed
that their properties depend from the structure of comꢀ
pounds.
chlorides with subsequent rearrangement of obtained esꢀ
ters 2 upon the action of a base with the formation of

ꢀdiketones 3. The reaction of compounds 3 with aromatꢀ
ic aldehydes led to the products of aldol condensation,
existing in two isomeric forms (4, 5), whose subseꢀ
quent oxidation gave rise to chromones 6a—e, having
the thiophene and furan rings at position 2 and the
fragments containing a methylꢀsubstituted phenyl or
Figure 1 shows an example of the absorption spectra of
the starting chromone 6a (curve 1), a photoproduct obꢀ
tained from it upon the action of UV irradiation (curve 2),
as well as a photoinduced fluorescence of this photoprodꢀ
uct (curve 3). Other synthesized compounds are characꢀ
terized by similar photoinduced changes of absorption and
luminescent properties.
2
ꢀthienyl group at position 3. The reaction of the latter
with Nꢀbromosuccinimide in the presence of dibenzoyl
Scheme 2
i. SeO , 1,4ꢀdioxane; ii. NBS, (PhCOO) , CCl , reflux.
2
2
4
2
, 3: R1 = 4ꢀMeC H (a), 5ꢀmethylthiophenꢀ2ꢀyl (b)
6 4
Compoꢀ
R1
X
R2
Compoꢀ
R1
X
R2
und 6
und 7
a
b
c
d
e
4ꢀMeC H
O
S
O
S
S
H
H
H
H
Me
a
b
c
d
e
4ꢀBrCH C H
O
S
O
S
S
H
H
H
H
6
4
4
2
6
4
4
4ꢀMeC H
4ꢀBrCH C H
6
2 6
5ꢀMethylthiophenꢀ2ꢀyl
5ꢀMethylthiophenꢀ2ꢀyl
5ꢀMethylthiophenꢀ2ꢀyl
5ꢀBrCH ꢀthiophenꢀ2ꢀyl
2
5ꢀBrCH ꢀthiophenꢀ2ꢀyl
2
5ꢀBrCH ꢀthiophenꢀ2ꢀyl
CH Br
2
2

Photosensitive 3ꢀacylꢀ2ꢀhetarylchromones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1763
Table 1. Conditions of the nucleophilic substitution reactions in compounds 8—10
Starting
compound
Nucleophile
Solvent
Base
T/C
Product
R
Yield
(%)
t
ButS
BuS
PhO
7
a
Bu SH
DMF
EtOH
DMF
DMF
K CO
60
~20
70
8a
8b
8c
8d
58
62
51
48
2
3
3
3
3
BuSH
PhOH
,4,5ꢀTrimethoxyꢀ
aniline
K CO
2
K CO
2
3
3
K CO
70
3,4,5ꢀTrimethoxyꢀ
phenylaminꢀ1ꢀyl
Morpholinꢀ4ꢀyl
2
Morpholine
DMF
DMF
EtOH
DMF
K CO
60
60
Reflux
70
8e
9a
9b
9c
71
67
49
44
2
3
3
t
t
7
7
b
d
Bu SH
K CO
Bu S
2
PhSNa
,4,5ꢀTrimethoxyꢀ
aniline
Morpholine
Morpholine
—
PhS
K CO
3,4,5ꢀTrimethoxyꢀ
phenylaminꢀ1ꢀyl
Morpholinꢀ4ꢀyl
Morpholinꢀ4ꢀyl
2
3
DMF
DMF
K CO
60
70
9d
10
61
54
2
3
3
K CO
2
In order to demonstrate the influence of structural facꢀ
tors on the spectral and kinetic characteristics, the experiꢀ
mental data obtained from the spectroscopic and kinetic
studies of the chromones synthesized are given in Table 2.*
Analysis of the experimental data given in Table 2
shows that all the compounds in the initial state are charꢀ
acterized by strong shortꢀwave absorption bands with the
maxima at 310—314 nm in the UV region of the spectrum.
Irradiation of solutions with the UV light transforms
chromones to the photoproducts absorbing and fluorescꢀ
ing in the visible region of the spectrum.
of the substituent at the carbonyl group causes a sharp
increase in the intensity of the fluorescence band. The
modification of the methyl group to the bromomethyl one
at position 5 of thiophene does not lead to considerable
changes in the absorption and fluorescence bands, howevꢀ
er, promotes improvement of the fluorescent properties.
The replacement of the furan fragment by the thiophene
(cf. compounds 8e and 9d) results in the significant shift of
A
Ifl (rel. units)
B
The nature of substituents in the phenyl fragment of
furylꢀsubstituted chromones (cf. compounds 6a and 8e)
virtually has no influence on position of the absorption
and fluorescence bands of the photoproduct. In this case,
a slight decrease in the fluorescence intensity of comꢀ
pound 8e is observed. The susceptibility of these comꢀ
1.6
2500
1
1
.4
.2
2000
1.0
1
1
5
500
000
00
0
0
0
.8
.6
.4
pounds to UV irradiation, evaluated by the parameter
ph

AB /A , turned out to be similar.
A
3
The replacement of the phenyl fragment by the thioꢀ
phene one (cf. compounds 6a and 7c) causes a bathochroꢀ
2
0.2
1
mic shift of the absorption (by 30 nm) and fluorescence
(by 20 nm) bands of the photoproduct. Such a replacement
300
400
500
600
/nm
Fig. 1. Absorption (1, 2) and fluorescence (3) spectra of comꢀ
pound 6a in toluene before (1) and after (2, 3) the exposure to
the UV irradiation. The fluorescence was recorded upon photo
excitation with the 420 nm wavelength light.
*
The full analysis of the results of spectral and kinetic studies of
all the chromones synthesized is planned to be published in the
journal Optics and Spectroscopy.

1
764
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Semenova et al.
Table 2. Spectral and kinetic absorption and fluorescent characꢀ
teristics of phototransformations of chromones in toluene
tion of the photoinduced form of compounds under study in
solution were performed on a Cary 50 (Varian) spectrophotomeꢀ
ter. Fluorescence spectra were recorded on a CARY ECLIPSE
Comꢀ Amax
pound

Bmax
Aph
/AA
Bfl,max
IBfl
(rel. units)
(Varian) spectrofluorimeter. Toluene (Aldrich) was used as
a solvent. The concentration of solutions was C = 4•10–5 mol L
.
–1
A 1ꢀcm thick quartz kuvette was used for the measurements. An
LCꢀ4 Hamamatsu lamp with a UV light filter was used for the
irradiation (photocoloring). The efficiency of compound photoꢀ
coloring was evaluated by the maximum value of the photoꢀ
induced optical density in the absorption band maximum of the
photoproduct in the photostationary state. It was determined
based on the kinetic curve of the dependence of optical density
from the irradiation time after the photostationary state was esꢀ
tablished and normalized by the value of optical density in the
absorption band maximum of the starting compound.
Acylation of 2´ꢀhydroxyacetophenones (general procedure).
Aromatic acyl chloride (24 mmol) was added in small portions to
2´ꢀhydroxyacetophenone 1 (20 mmol) dissolved in anhydrous
pyridine (15 mL) at <10 C. After the addition was completed,
the mixture was kept for 1 h at ~20 C, poured in water, and
stirred until the oil formed crystallized. The precipitate obtained
was filtered off, washed with cold water and recrystallized from
ethanol (or washed with ethanol).
6
8
7
9
1
7
а
e
с
d
0
d
313
313
308
314
310
310
30000
22500
45000
20000
30000
40000
420
420
450
400
425
440
0.2
0.2
0.2
0.1
0.1
0.2
500
500
520
495
520
510
540
470
1460
70
230
670
Note. max and Bmax are the wavelengths (nm) of the absorption
band maxima of the starting (A) and photoinduced (B) forms,
respectively; B
band maximum of photoproduct B;  (L mol cm ) is the molar
extinction; AB /A is the photoinduced change in the value of
optical density in the absorption band maximum of the photoꢀ
induced form in the photostationary state normalized by the
value of optical density in the absorption band maximum of the
fl,max
is the wavelength (nm) of the fluorescence
–1
–1
ph
A
fl
starting open form A; IB is the intensity of the fluorescence in
the fluorescence band maximum in the photostationary state.
2
ꢀAcetylphenyl 4´ꢀmethylbenzoate (2a). The yield was 90%,
1
m.p. 99—101 C (EtOH). H NMR (CDCl ), : 8.13 (d, 2 H,
3
the absorption band of the photoproduct (by 20 nm) and
the small shift of the fluorescence band (by 5 nm) to the
shortꢀwave spectral region. However, the light sensitivity
of the compound falls to one half and the intensity of the
fluorescence band is sharply dropped.
J = 8.0 Hz); 7.87 (d, 1 H, J = 7.5 Hz); 7.57 (t, 1 H, J = 7.5 Hz);
7.20—7.41 (m, 4 H); 2.45 (s, 3 H); 2.56 (s, 3 H). C NMR
13
(75.47 MHz, CDCl ), : 197.67, 165.23, 149.58, 144.84, 133.39,
3
1
31.60, 130.45 (2 C); 130.26, 129.53 (2 C); 126.60, 126.15,
1
24.02, 29.95, 21.84. Found (%): C, 75.59; H, 5.60. C H O .
16 14
3
Calculated (%): C, 75.57; H, 5.55.
Interestingly to note that the introduction of bromine
in the methyl fragment of 2ꢀthienylꢀ3ꢀ(5ꢀmethylthiophenꢀ
2
ꢀAcetylphenyl 5´ꢀmethylthiopheneꢀ2ꢀcarboxylate (2b). The
1
yield was 94%, m.p. 108—109 C (EtOH). H NMR (CDCl ), :
3
2
ꢀylcarbonyl)chromone (6d) gives the bromomethyl deꢀ
rivative with fluorescent properties considerably enhanced
compound 7d), providing its practically acceptable charꢀ
acteristics.
In conclusion, the design of the chromones synthesꢀ
7
.81—7.88 (m, 2 H); 7.57 (t, 1 H, J = 7.7 Hz); 7.35 (t, 1 H,
J = 7.5 Hz); 7.23 (d, 1 H, J = 8.0 Hz); 6.87 (d, 1 H, J = 3.4 Hz);
(
13
2
.52—2.58 (m, 6 H). C NMR (75.47 MHz, CDCl ), : 197.62,
3
160.31, 149.97, 149.14, 135.78, 133.31, 131.58, 130.22, 129.72,
126.97, 126.21, 123.95, 30.14, 15.93. Found (%): C, 64.67;
H, 4.63; S, 12.28. C H O S. Calculated (%): C, 64.60; H, 4.65;
ized provides a possibility of a fine adjustment of properꢀ
ties of photofluorescent compounds in order to meet reꢀ
quirements of the lightꢀsensitive recording media with the
fluorescent reading of optical information designated for
the development of multilayer optical disk with 3 D optiꢀ
cal memory of the archive type.
14 12
3
S, 12.32.
Synthesis of ꢀdiketone derivatives (general procedure). Anꢀ
t
hydrous Bu OK (31.4 mmol) was added to 2ꢀacyloxyacetopheꢀ
none 2 (15.7 mmol) in dry DMF (20 mL) with cooling (T < 0 C).
The reaction mixture was kept at 0—10 C. After the reaction
reached completion (TLC monitoring), the mixture was poured
in water with ice and 30% aqueous hydrochloric acid was added
in small portions to it. A precipitate of the product was filtered
off and recrystallized from ethanol (or washed with ethanol).
1ꢀ(2ꢀHydroxyphenyl)ꢀ3ꢀ(4ꢀmethylphenyl)propaneꢀ1,3ꢀdione
Experimental
1H NMR spectra were recorded on Bruker ACꢀ200 (200 MHz)
1
and Bruker AMꢀ300 (300 MHz) spectrometers in CDCl ,
(3a). The yield was 76%, m.p. 106—107 C (EtOH). H NMR
3
13
C NMR spectra on a Bruker AMꢀ300 (75 MHz) spectrometer
(CDCl ), : 15.63 (s, 1 HOH); 12.16 (s, 1 HOH); 7.87 (dd, 2 H,
3
in CDCl , using signals of residual protons and carbon atoms of
J = 8.0 Hz); 7.78 (d, 1 H, J = 7.8 Hz); 7.45 (t, 1 H, J = 7.75 Hz);
3
the solvent as references. Mass spectra were measured on a Varian
MAT CHꢀ6 instrument (70 eV) with direct injection of samples
into the source of irradiation, control voltage of 1.75 kV. Melting
points were measured on a Boetius heating stage and were not
corrected. The progress of all the reactions and purities of comꢀ
pounds isolated were carried out by TLC on Merck Silica gel 60
F254 UVꢀ254 plates.
7.28 (d, 2 H, J = 7.9 Hz); 7.01 (d, 1 H, J = 8.2 Hz); 6.92 (t, 1 H,
J = 7.4 Hz); 6.80 (s, 1 Htw.fr); 2.43 (s, 3 H). C NMR
1
3
(75.47 MHz, CDCl ), : 195.44, 177.90, 162.52, 143.41, 135.74,
3
129.66, 129.60 (2 C), 128.58, 126.94 (2 C), 119.36, 119.14,
118.84, 91.83, 21.72. Found (%): C, 75.50; H, 5.73. C H O .
16
14
3
Calculated (%): C, 75.57; H, 5.55.
1ꢀ(2ꢀHydroxyphenyl)ꢀ3ꢀ(5ꢀmethylthiophenꢀ2ꢀyl)propaneꢀ
Spectrophotometric measurements (photostationary spectra)
of kinetics of the processes of photocoloring and photodegradaꢀ
1,3ꢀdione (3b). The yield was 70%, m.p. 79—81 C (EtOH).
1
H NMR (DMSOꢀd ), : 11.35 (s, 1 H); 10.93 (s, 1 H); 7.85—7.92
6

Photosensitive 3ꢀacylꢀ2ꢀhetarylchromones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1765
(
(
1
m, 3 H); 7.45 (m, 1 H); 6.99 (m, 3 H); 2.5 (s, 3 H). MS, m/z
Irel (%)): 260 [M] (87), 125 [M – Me – C H S – CO] (100),
4 3
21 [Ph(CO)O]+ (59). Found (%): C, 64.75; H, 4.61; S, 12.26.
(s, 1 HOH); 7.88 (d, 1 H, J = 7.9 Hz); 7.38 (t, 1 H, J = 7.5 Hz);
7.20 (d, 1 H, J = 3.7 Hz); 7.03 (t, 1 H, J = 7.5 Hz); 6.90 (d, 1 H,
J = 8.3 Hz); 6.83 (d, 1 H, J = 3.1 Hz); 6.75 (d, 1 H, J = 3.4 Hz);
6.72 (s, 1 H); 6.52 (m, 1 H); 2.52 (s, 3 H); 2.39 (s, 3 H). 1 C NMR
+
+
3
C H O S. Calculated (%): C, 64.60; H, 4.65; S, 12.32.
14
12
3
Reaction of aromatic aldehydes with ꢀdiketones (general proꢀ
(75.47 MHz, CDCl ), : 179.15, 176.12, 156.57, 148.35, 142.04,
3
cedure). A solution of 1,3ꢀdiketone 3 (5.51 mmol), aromatic
aldehyde (6.6 mmol), and a drop of piperidine in ethanol (10 mL)
was stirred for 4—8 days at ~20 C. After the reaction reached
completion (TLC monitoring), the solvent was evaporated on
a rotary evaporator and recrystallized from ethanol or purified
using filtration of the solution of compound in dichloromethane
through silica gel. A mixture of cyclic and linear forms of the
products (4d, 5d) was used in the reaction without separation. In
other cases, only linear or only cyclic form was isolated.
141.29, 136.23, 135.08, 132.54, 127.96, 127.03, 126.09, 124.98,
122.01, 120.67, 118.06, 103.51, 72.79, 15.72, 15.54. Found (%):
C, 65.29; H, 4.26; S, 17.48. C20H16O S . Calculated (%):
3
2
C, 65.19; H, 4.38; S, 17.40.
Synthesis of 2ꢀhetarylꢀ3ꢀacylchromones 6a—e (general proꢀ
cedure). The product of the aldol condensation of compound 4
(5) (4.1 mmol) and selenium dioxide (1.41 g, 12.71 mmol) was
refluxed for 6—8 h in 1,4ꢀdioxane (10 mL). After the reaction
reached completion (TLC monitoring), dioxane was evaporatꢀ
ed, the residue was dissolved in dichloromethane, and the soluꢀ
tion was passed through a layer of silica gel. Dichloromethane
was evaporated on a rotary evaporator. The residue was washed
with ethanol on the filter.
3
ꢀ(4ꢀMethylbenzoyl)ꢀ2ꢀ(furanꢀ2ꢀyl)ꢀ2,3ꢀdihydrochromenꢀ4ꢀ
1
one (5a). The yield was 74%, m.p. 145—147 C. H NMR
CDCl ), : 7.92 (d, 1 H, J = 7.8 Hz); 7.87 (d, 2 H, J = 8.0 Hz);
(
3
7
7
6
.54 (t, 1 H, J = 7.5 Hz); 7.37 (s, 1 H); 7.26 (d, 2 H, J = 7.8 Hz);
.02—7.12 (m, 2 H); 6.43—6.47 (m, 1 H); 6.29—6.34 (m, 1 H);
.03 (d, 1 H, J = 11.0 Hz); 5.32 (d, 1 H, J = 11.0 Hz); 2.42 (s, 3 H).
2ꢀ(Furanꢀ2ꢀyl)ꢀ3ꢀ(4ꢀmethylbenzoyl)ꢀ4Hꢀchromenꢀ4ꢀone (6a).
1
The yield was 62%, m.p. 184—185 C. H NMR (CDCl ),
3
1
3
C NMR (75.47 MHz, CDCl ), : 192.72, 189.22, 160.66,
: 8.25 (d, 1 H, J = 7.8 Hz); 7.90 (d, 2 H, J = 8.2 Hz); 7.75 (t, 1 H,
J = 8.3 Hz); 7.57 (d, 1 H, J = 8.4 Hz); 7.44 (t, 1 H, J = 7.5 Hz);
7.20—7.28 (m, 3 H); 7.14 (d, 1 H, J = 3.4 Hz); 6.49—6.53 (m, 1 H);
3
1
1
2
49.83, 144.83, 143.50, 136.73, 134.83, 129.60 (2 C), 129.35(2 C),
27.42, 122.03, 120.71, 118.23, 110.72, 110.52, 74.31, 56.42,
1.77. Found (%): C, 75.66; H, 5.03. C H O . Calculated (%):
13
2.4 (s, 3 H). C NMR (50.32 MHz, CDCl ), : 192.29, 176.22,
21
16
4
3
C, 75.89; H, 4.85.
155.58, 151.31, 146.58, 145.32, 144.68, 134.75, 134.32, 129.46,
3
ꢀ(4ꢀMethylbenzoyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ2,3ꢀdihydrochromꢀ
126.03, 125.99, 125.53, 123.52, 119.24, 117.95, 115.83, 112.42,
1
+
+
enꢀ4ꢀone (5b). The yield was 80%, m.p. 163—165 C. H NMR
CDCl ), : 7.82 (d, 1 H, J = 7.4 Hz); 7.71 (d, 2 H, J = 7.9 Hz);
.55 (t, 1 H, J = 7.4 Hz); 7.18—7.30 (m, 3 H); 7.02—7.16 (m, 3 H);
21.82. MS, m/z (I (%)): 330 [M] (48), 301 [M – HCO] (8),
rel
+
+
(
7
120 [Ph(CO)O] (36), 92 [PhO] (100). Found (%): C, 76.44;
H, 4.32. C H O . Calculated (%): C, 76.36; H, 4.28.
3
21
14
4
6
.92 (t, 1 H, J = 4.0 Hz); 6.27 (d, 1 H, J = 11.1 Hz); 5.15 (d, 1 H,
3ꢀ(4ꢀMethylbenzoyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ4Hꢀchromenꢀ4ꢀone
13
1
J = 11.1 Hz); 2.41 (s, 3 H). C NMR (75.47 MHz, CDCl ),
(6b). The yield was 76%, m.p. 186—188 C. H NMR (CDCl ),
3
3

(
1
: 194.97, 189.17, 160.69, 144.75, 140.12, 136.71, 135.05, 129.50
2 C), 128.94 (2 C), 127.44, 127.28, 126.87, 126.47, 122.08,
20.69, 118.26, 77.27, 60.06, 21.71. Found (%): C, 72.25; H, 4.60;
S, 8.99. C H O S. Calculated (%): C, 72.39; H, 4.63; S, 9.20.
: 8.25 (d, 1 H, J = 8.0 Hz); 7.85 (d, 2 H, J = 8.1 Hz); 7.75 (t, 1 H,
J = 7.9 Hz); 7.42—7.61 (m, 4 H); 7.21—7.28 (m, 2 H); 7.03
(t, 1 H, J = 4.4 Hz); 2.40 (s, 3 H). C NMR (75.47 MHz,
13
CDCl ), : 193.36, 176.32, 155.82, 155.58, 145.26, 134.34,
21
16
3
3
1
ꢀ(2ꢀHydroxyphenyl)ꢀ3ꢀ(5ꢀmethylthiopheneꢀ2ꢀcarbonyl)ꢀ2ꢀ
134.30, 133.40, 131.55, 131.44, 129.73, 129.66, 128.42, 126.03,
(
1
furanꢀ2ꢀyl)propꢀ2ꢀenꢀ1ꢀone (4c). The yield was 85%, m.p.
125.60, 123.27, 120.37, 118.01, 21.86. MS, m/z (I (%)): 346
rel
1
+
+
+
46—148 C (EtOH). H NMR (CDCl ), : 17.32 (s, 1 H); 7.91
[M] (71), 317 [M – HCO] (100), 120 [Ph(CO)O] (27), 92
3
+
(
7
d, 1 H, J = 8.0 Hz); 7.85 (d, 1 H, J = 7.8 Hz); 7.34—7.47 (m, 2 H);
.08 (m, 2 H); 6.89 (m, 1 H); 6.74 (d, 1 H, J = 3.5 Hz); 6.62
s, 1 H); 6.30 (m, 1 H); 2.53 (s, 3 H). MS, m/z (I (%)): 338
[PhO] (88). Found (%): C, 72.95; H, 4.14; S, 9.41. C H O S.
21
14
3
Calculated (%): C, 72.81; H, 4.07; S, 9.26.
(
[
2ꢀ(Furanꢀ2ꢀyl)ꢀ3ꢀ(5ꢀmethylthiopheneꢀ2ꢀcarbonyl)ꢀ4Hꢀchromꢀ
rel
+
+
+
1
M] (11), 310 [M – CO] (8), 214 [M – CH C H SCO] (29),
enꢀ4ꢀone (6c). The yield was 74%, m.p. 178—180 C. H NMR
3
+
4
2
+
1
28 [CH C H SCO] (100), 97 [CH C H S] (75). Found (%):
(CDCl ), : 8.25 (d, 1 H, J = 7.9 Hz); 7.75 (t, 1 H, J = 7.3 Hz);
3
4
2
3
4
2
3
C, 67.29; H, 4.11; S, 9.62. C H O S. Calculated (%): C, 67.44;
H, 4.17; S, 9.48.
7.39—7.61 (m, 4 H); 7.15 (d, 1 H, J = 3.3 Hz); 6.75 (m, 1 H);
19
14
4
13
6.55 (m, 1 H); 2.55 (s, 3 H). C NMR (50.32 MHz, CDCl ),
3
A mixture of 1ꢀ(2ꢀhydroxyphenyl)ꢀ3ꢀ(5ꢀmethylthiopheneꢀ2ꢀ
carbonyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)propꢀ2ꢀenꢀ1ꢀone (4d) and 3ꢀ(5ꢀmeꢀ
thylthiopheneꢀ2ꢀcarbonylꢀ2ꢀthiophenꢀ2ꢀyl)ꢀ2,3ꢀdihydrochromenꢀ
: 183.84, 175.88, 155.52, 151.54, 151.32, 146.74, 145.17, 142.28,
135.14, 134.36, 127.12, 126.14, 125.58, 123.56, 119.04, 117.97,
116.15, 112.51, 16.26. MS, m/z (I (%)): 336 [M]+ (95), 308
rel
+
+
+
4
ꢀone (5d). The yield was 62%, m.p. 117—118 C (EtOH).
[M – CO] (51), 282 [M – C H O] (27), 113 [M – C H O S]
3 2 12 9 3
(76), 92 [PhO] (100). Found (%): C, 67.89; H, 3.67; S, 9.21.
C H O S. Calculated (%): C, 67.85; H, 3.60; S, 19.03.
1
+
H NMR (CDCl ), : 17.21 (s, 1 HOH); 7.88 (d, 1 H, J = 7.9 Hz);
3
7
.38 (t, 1 H, J = 7.5 Hz); 7.20 (d, 1 H, J = 3.7 Hz); 7.03 (t, 1 H,
19
12
4
J = 7.5 Hz); 6.90 (d, 1 H, J = 8.3 Hz); 6.83 (d, 1 H, J = 3.1 Hz);
3ꢀ(5ꢀMethylthiopheneꢀ2ꢀcarbonyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ4Hꢀ
6
2
.75 (d, 1 H, J = 3.4 Hz); 6.72 (s, 1 H); 6.52 (m, 1 H); 2.52 (s, 3 H);
chromenꢀ4ꢀone (6d). The yield was 89%, m.p. 180—182 C.
13
1
.39 (s, 3 H). C NMR (75.47 MHz, CDCl ), : 179.15, 176.12,
H NMR (CDCl ), : 8.25 (d, 1 H, J = 7.9 Hz); 7.75 (t, 1 H,
3
3
1
1
1
56.57, 148.35, 142.04, 141.29, 136.23, 135.08, 132.54, 127.96,
27.03, 126.09, 124.98, 122.01, 120.67, 118.06, 103.51, 72.79,
5.72, 15.54. Found (%): C, 65.29; H, 4.26; S, 17.48. C H O S .
J = 7.3 Hz); 7.55—7.65 (m, 3 H); 7.40—7.50 (m, 2 H); 7.05
(t, 1 H, J = 4.3 Hz); 6.75 (d, 1 H, J = 3.5 Hz); 2.55 (s, 3 H).
13
C NMR (75.47 MHz, CDCl ), : 184.73, 175.93, 155.77,
3
20
16
3
2
Calculated (%): C, 65.19; H, 4.38; S, 17.40.
155.71, 152.16, 141.92, 135.60, 134.31, 133.32, 131.71, 131.57,
128.49, 127.34, 126.11, 125.61, 123.32, 120.19, 117.98, 16.28.
Found (%): C, 64.75; H, 3.41; S, 18.30. C H O S . Calculatꢀ
1
ꢀ(2ꢀHydroxyphenyl)ꢀ3ꢀ(5ꢀmethylthiopheneꢀ2ꢀcarbonyl)ꢀ2ꢀ
(
6
5ꢀmethylthiophenꢀ2ꢀyl)propꢀ2ꢀenꢀ1ꢀone (4e). The yield was
2%, m.p. 117—118 C (EtOH). H NMR (CDCl ), : 17.21
19
12
3 2
1
ed (%): C, 64.75; H, 3.43; S, 18.20.
3

1
766
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Semenova et al.
+
3
ꢀ(5ꢀMethylthiopheneꢀ2ꢀcarbonyl)ꢀ2ꢀ(5ꢀmethylthiophenꢀ2ꢀ
[PhO] (100). Found (%): C, 53.01; H, 2.60; Br, 18.45; S, 14.90.
C H BrO S . Calculated (%): C, 52.91; H, 2.57, Br, 18.53;
yl)ꢀ4Hꢀchromenꢀ4ꢀone (6e). The yield was 74%, m.p. 184—185 C.
H NMR (CDCl ), : 8.21 (d, 1 H, J = 7.9 Hz); 7.23 (t, 1 H,
19
11
3 2
1
S, 14.87.
3
J = 7.7 Hz); 7.51—7.56 (d, 1 H, J = 8.4 Hz); 7.39—7.49 (m, 3 H);
6
3ꢀ(5ꢀBromomethylthiopheneꢀ2ꢀcarbonyl)ꢀ2ꢀ(5ꢀbromomethꢀ
.72—6.77 (m, 2 H); 2.49 (s, 3 H); 2.51 (s, 3 H). 13C NMR
ylthiophenꢀ2ꢀyl)ꢀ4Hꢀchromenꢀ4ꢀone (7e). The yield was 89%,
1
(
75.47 MHz, CDCl ), : 185.02, 175.91, 155.92, 155.70, 151.99,
m.p. 90—92 C. H NMR (CDCl ), : 8.22 (d, 1 H, J = 7.9 Hz);
3
3
1
1
47.51, 142.06, 135.54, 134.17, 132.31, 130.66, 127.33, 127.18,
26.11, 125.48, 123.36, 119.44, 117.89, 16.31, 15.62. Found (%):
7.72—7.79 (m, 1 H); 7.53—7.61 (m, 1 H); 7.38—7.51 (m, 3 H);
7.04—7.09 (m, 2 H); 4.67 (s, 2 H); 4.65 (s, 2 H). C NMR
13
C, 64.56; H, 3.83; S, 18.53. C20H O S . Calculated (%):
(75.47 MHz, CDCl ), : 185.13, 175.69, 155.75, 155.71, 150.89,
14
3
2
3
C, 65.55; H, 3.85; S, 17.50.
147.13, 144.52, 134.84, 134.66, 133.92, 131.87, 129.38, 129.23,
Synthesis of bromomethylꢀsubstituted chromones (general proꢀ
cedure). A mixture of compound 6 (0.87 mmol) with Nꢀbromoꢀ
succinimide (0.18 g, 1.044 mmol)) and catalytic amount of diꢀ
benzoyl peroxide in carbon tetrachloride (10 mL) was refluxed
for 4—9 h (TLC monitoring). After the reaction reached comꢀ
pletion, the solution was diluted with light petroleum (1 : 1) and
filtered through a layer of silica gel. The solution obtained was
concentrated on a rotary evaporator and the residue was recrysꢀ
tallized from a mixture of acetone—light petroleum (1 : 1).
126.17, 125.93, 123.29, 120.19, 117.99, 25.37, 25.22. MS, m/z
+
+
(Irel (%)): 524 [M] (33), 446 (32) 445 (82), 444 [M – Br] (75),
+
+
365 (16), 364 [M – 2 Br] (89), 363 (63), 268 [M – C H BrS]
5
5
(85), 192 (85), 149 (100). Found (%): C, 45.75; H, 2.34; Br, 30.54.
C H Br O S . Calculated (%): C, 45.82; H, 2.31, Br, 30.48.
2
0
12
2
3 2
Reaction of 3ꢀ(4ꢀbromomethylbenzoyl)ꢀ2ꢀhetarylꢀ4Hꢀchromꢀ
enꢀ4ꢀones 7a,b with mercaptanes (general procedure). A mixture
t
of compound 7 (0.27 mmol) and Bu SH (0.128 g, 1.42 mmol) in
DMF (3 mL) was stirred with mild heating (T < 60 C) in the
3
ꢀ(4ꢀBromomethylbenzoyl)ꢀ2ꢀ(furanꢀ2ꢀyl)ꢀ4Hꢀchromenꢀ4ꢀ
presence of K CO3 (0.045 g, 0.324 mmol). After the reaction
2
1
one (7a). The yield was 41%, m.p. 189—191 C. H NMR
CDCl ), : 8.18 (d, 1 H, J = 8.1 Hz); 7.95 (d, 2 H, J = 7.8 Hz);
.75 (t, 1 H, J = 7.1 Hz); 7.41—7.60 (m, 5 H); 7.18 (d, 1 H,
J = 3.3 Hz); 6.51 (m, 1 H); 4.49 (s, 2 H). C NMR (50.32 MHz,
CDCl ), : 192.04, 176.27, 155.60, 146.80, 145.24, 143.29,
36.93, 134.48, 129.81 (2 C); 129.51 (2 C); 127.15, 126.02,
25.67, 123.46, 118.79, 117.99, 115.99, 112.55, 32.39. MS, m/z
Irel (%)): 409 [M] (15), 329 [M – Br]+ (73), 119 [Ph(CO)O]
reached completion (TLC monitoring), the mixture was poured
in water. A precipitate formed was filtered off, washed with waꢀ
ter, dissolved in dichloromethane, and filtered through a layer of
silica gel. After concentration on a rotary evaporator, the residue
was recrystallized from hexane to give the product 8a or 9a.
3ꢀ(4ꢀtertꢀButylthiomethylbenzoyl)ꢀ2ꢀ(furanꢀ2ꢀyl)ꢀ4Hꢀchromꢀ
(
7
3
13
3
1
1
(
(
1
enꢀ4ꢀone (8a). The yield was 58%, m.p. 166—168 C. H NMR
+
+
(CDCl ), : 8.19 (d, 1 H, J = 7.9 Hz); 7.92 (d, 2 H, J = 8.1 Hz);
3
+
100), 92 [PhO] (48). Found (%): C, 61.51; H, 3.19; Br, 19.54.
7.68 (t, 1 H, J = 7.3 Hz); 7.55 (d, 1 H, J = 8.4 Hz); 7.37—7.45
C H BrO . Calculated (%): C, 61.63; H, 3.20; Br, 19.53.
(m, 4 H); 7.13 (d, 1 H, J = 3.5 Hz); 6.48 (m, 1 H); 3.79 (s, 2 H);
21
13
4
13
3
ꢀ(4ꢀBromomethylbenzoyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ4Hꢀchromenꢀ
1.32 (s, 9 H). C NMR (75.47 MHz, CDCl ), : 192.15, 176.19,
3
1
4
ꢀone (7b). The yield was 62%, m.p. 175—177 C. H NMR
155.61, 151.39, 146.77, 146.62, 145.23, 135.86, 134.36, 129.76
(
CDCl ), : 8.21 (d, 1 H, J = 8.0 Hz); 7.96 (d, 2 H, J = 7.5 Hz);
(2 C); 129.39 (2 C); 126.02, 125.55, 123.56, 119.13, 118.13,
3
7
4
5 (t, 1 H, J = 7.2 Hz); 7.39—7.66 (m, 6 H); 7.03 (t, 1 H, J = 4.5 Hz);
115.87, 112.46, 43.27, 33.41, 30.95 (3 C). MS, m/z (I (%)): 418
[M] (87), 362 [M – Bu ] (20), 329 [M – S – Bu ] (67), 239
rel
t +
+
+
t +
.48 (s, 2 H). MS, m/z (I (%)): 426 [M] (5), 424 (4), 345
rel
+
+
+
t
+
t
+
[
(
[
M – Br] (15), 341 [M – C H S] (54), 306 [M – C H Br]
28), 279 [M – C H BrCO] (39), 92 [C H O] (47), 84
C H S] (14). Found (%): C, 59.22; H, 3.11; Br, 18.43.
[M – Bu – S – CH Ph] (88), 255 [M – Bu – S – CH PhO]
2 2
4
3
3
3
+
+
+
t
+
+
(38), 121 [Ph(CO)O] (26), 101 [Bu SCH] (53), 92 [PhO]
(39), 73 [SC(CH3)2] (100). Found (%): C, 71.72; H, 5.33;
S, 7.76. C H O S. Calculated (%): C, 71.75; H, 5.30; S, 7.66.
3
3
6
4
+
+
4
4
C H BrO S. Calculated (%): C, 59.31; H, 3.08, Br, 18.79.
21
13
3
25 22
4
3
ꢀ(5ꢀBromomethylthiopheneꢀ2ꢀcarbonyl)ꢀ2ꢀ(furanꢀ2ꢀyl)ꢀ4Hꢀ
3ꢀ(4ꢀtertꢀButylthiomethylbenzoyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ4Hꢀ
chromenꢀ4ꢀone (9a). The yield was 67%, m.p. 133—136 C.
chromenꢀ4ꢀone (7c). The yield was 52%, m.p. 132—134 C.
H NMR (CDCl ), : 8.23 (d, 1 H, J = 7.9 Hz); 7.65—7.68
1
1
H NMR (CDCl ), : 8.20 (d, 1 H, J = 7.7 Hz); 7.95 (d, 2 H,
3
3
(
7
(
t, 1 H, J = 7.4 Hz); 7.48—7.61 (m, 4 H); 7.2 (d, 1 H, J = 3.4 Hz);
.05 (d, 1 H, J = 3.6 Hz); 6.55 (m, 1 H); 4.65 (s, 2 H). 13C NMR
50.32 MHz, CDCl ), : 184.20, 175.77, 155.43, 151.68, 149.79,
J = 8.1 Hz); 7.75 (t, 1 H, J = 7.1 Hz); 7.39—7.61 (m, 6 H); 7.02
(t, 1 H, J = 4.3 Hz); 3.78 (s, 2 H); 1.33 (s, 9 H). C NMR
13
(75.47 MHz, CDCl ), : 193.25, 176.28, 155.82, 155.69, 145.77,
3
3
1
46.92, 144.97, 144.88, 134.47, 134.14, 128.95, 125.98, 125.66,
135.29, 134.36, 133.31, 131.60, 131.5, 129.78 (2 C); 129.59
1
4
23.41, 118.34, 117.97, 116.29, 112.58, 25.56. MS, m/z (I (%)):
(2 C); 128.45, 126.06, 125.63, 123.26, 120.24, 118.02, 43.28, 33.41,
30.96 (3 C). MS, m/z (I (%)): 434 [M] (25), 378 [M – Bu ]
rel
rel
+
+
+
t +
14 [M] (3), 337 (30), 336 (37), 335 [M – Br] (100), 307 [M –
+
+
+
t +
t
+
–
(
COBr] (33), 282 [M – C H OBr] (40), 239 [M – C H BrS]
(46), 345 [M – S – Bu ] (22), 293 [M – Bu – S – CH C H ] (63),
2 3 2
3
2
5
4
16), 119 [Ph(CO)O]+ (81), 92 [C H O] (32). Found (%):
+
255 [M – Bu – S – CH Ph] (100), 197 [M – C H CH SBu –
2 6 4 2
– C H S] (18), 167 [M – C H CH SBu – C H S – CH O]
2 2 6 4 2 2 2 2
(23), 92 [PhO] (40). Found (%): C, 69.13; H, 5.13; S, 14.72.
C H O S . Calculated (%): C, 69.10; H, 5.10; S, 14.76.
t
+
t
6
4
+
t
+
C, 54.91; H, 2.66; Br, 19.17; S, 7.83. C H BrO S. Calculatꢀ
19
11
4
+
ed (%): C, 54.96; H, 2.67, Br, 19.24; S, 7.72.
ꢀ(5ꢀBromomethylthiopheneꢀ2ꢀcarbonyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ
Hꢀchromenꢀ4ꢀone (7d). The yield was 74%, m.p. 145—147 C.
3
2
5
22
3 2
4
3ꢀ(4ꢀButylthiomethylbenzoyl)ꢀ2ꢀ(furanꢀ2ꢀyl)ꢀ4Hꢀchromenꢀ
1
H NMR (CDCl ), : 8.22 (d, 1 H, J = 7.8 Hz); 7.76 (t, 1 H,
4ꢀone (8b). A mixture of butylmercaptane (0.053 g, 0.587 mmol)
and potassium carbonate (0.1 g, 0.725 mmol) in ethanol (5 mL)
was stirred for 30 min at ~20 C, followed by the addition of
compound 7a (0.08 g, 0.195 mmol), and the reaction mixture
was stirred until the reaction reached completion (TLC moniꢀ
toring). Ethanol was evaporated, the residue was dissolved in
dichloromethane and the solution obtained was passed through
3
J = 7.6 Hz); 7.55—7.62 (m, 3 H); 7.43—7.51 (m, 2 H); 7.03—7.11
m, 2 H); 4.65 (s, 2 H). 1 C NMR (75.47 MHz, CDCl ),
3
(
3

: 184.13, 175.91, 156.10, 155.75, 150.65, 144.48, 134.68, 134.49,
1
1
3
32.03, 131.96, 131.88, 128.66, 128.60, 128.07, 126.12, 125.79,
+
23.27, 118.05, 25.36. MS, m/z (Irel (%)): 431 [M] (3), 353 (3),
52 (6), 351 [M – Br]+ (63), 256 [M – C H BrS] (72), 92
+
4
3

Photosensitive 3ꢀacylꢀ2ꢀhetarylchromones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1767
1
a layer of silica gel. After evaporation of the solvent, the pure
product (0.051 g, 62%) was obtained, m.p. 99—101 C. H NMR
159—161 C. H NMR (CDCl ), : 8.19 (d, 1 H, J = 7.6 Hz);
3
1
7.97 (d, 2 H, J = 7.9 Hz); 7.75 (t, 1 H, J = 7.6 Hz); 7.57 (d, 1 H,
J = 8.4 Hz); 7.35—7.51 (m, 4 H); 7.17 (d, 1 H, J = 3.4 Hz); 6.53
(m, 1 H); 5.97 (s, 2 H); 4.38 (s, 2 H); 3.77 (s, 9 H). 1 C NMR
(
CDCl ), : 8.21 (d, 1 H, J = 7.8 Hz); 7.94 (d, 2 H, J = 8.1 Hz);
3
3
7
3
.74 (m, 1 H); 7.27—7.56 (m, 5 H); 7.16 (s, 1 H); 6.51 (s, 1 H);
.71 (s, 2 H); 2.40 (s, 2 H); 1.53 (s, 2 H); 1.57 (s, 2 H); 0.87 (s, 3 H).
(75.47 MHz, CDCl ), : 192.14, 176.19, 155.56, 153.97 (2 C);
3
1
3
C NMR (50.32 MHz, CDCl ), : 192.17, 176.25, 155.61,
151.40, 146.56, 145.58, 145.27, 144.27, 136.32, 134.38, 129.76,
129.68 (2 C); 127.72 (2 C); 125.94, 125.57, 123.44, 118.97,
117.95, 115.86, 112.47, 91.01 (2 C); 61.05 (CpꢀOMe); 55.97
(2 CmꢀOMe); 48.72. MS, m/z (I (%)): 511 [M]+ (35), 329
3
1
1
1
51.41, 146.65, 145.32, 145.11, 135.91, 134.40, 129.61 (2 C);
29.25 (2 C); 126.06, 125.59, 123.52, 119.08, 117.98, 115.68,
12.48, 36.21, 31.27 (2 C), 21.99, 13.73. MS, m/z (I (%)): 418
rel
rel
M] (100), 329 [M – S – Bu]+ (97), 90 [SC H ] (25), 57
+
+
[M – (MeO) C H NH] (72). Found (%): C, 70.50; H, 4.88;
+
[
4
10
3
6
2
+
[
Bu] (54). Found (%): C, 71.70; H, 5.35; S, 7.75. C H O S.
N, 2.71. C H NO . Calculated (%): C, 70.44; H, 4.93; N, 2.74.
30 25 7
2
5
22
4
Calculated (%): C, 71.75; H, 5.30; S, 7.66.
2ꢀ(Thiophenꢀ2ꢀyl)ꢀ3ꢀ{4ꢀ[(3,4,5ꢀtrimethoxyphenylamino)ꢀ
3
ꢀ(4ꢀPhenylthiomethylbenzoyl)ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ4Hꢀchromꢀ
methyl]benzoyl}ꢀ4Hꢀchromenꢀ4ꢀone (9c). The yield was 44%,
1
enꢀ4ꢀone (9b). A mixture of compound 7b (0.106 g, 0.25 mmol)
m.p. 146—149 C. H NMR (CDCl ), : 8.18 (d, 1 H, J = 7.8 Hz);
3
and sodium thiophenolate (0.0362 g, 0.27 mmol) in ethanol
7.97 (d, 2 H, J = 7.9 Hz); 7.76 (t, 1 H, J = 7.4 Hz); 7.39—7.61
(
7 mL) was refluxed until the reaction reached completion (TLC
(m, 6 H); 7.03 (t, 1 H, J = 4.3 Hz); 5.87 (s, 2 H); 4.34 (s, 2 H);
13
monitoring). The solvent was evaporated, the residue was disꢀ
solved in dichloromethane and the solution formed was passed
through a layer of silica gel. After concentration on a rotary
evaporator, the residue was recrystallized from ethanol. The yield
was 49%, m.p. 176—178 C. H NMR (CDCl ), : 8.22 (d, 1 H,
J = 7.7 Hz); 7.95 (d, 2 H, J = 8.1 Hz); 7.75 (t, 1 H, J = 7.2 Hz);
3.73 (s, 9 H). C NMR (75.47 MHz, CDCl ), : 193.27, 176.29,
3
155.57, 155.67, 153.99 (2 C); 145.87, 143.85, 135.80, 134.89,
133.25, 131.53 (2 C); 131.12, 129.87 (2 C); 128.36, 127.99 (2 C);
125.93, 125.64, 123.15, 120.11, 117.89, 91.23 (2 C); 61.05
1
(CpꢀOMe); 55.98 (2 CmꢀOMe); 48.89. MS, m/z (I (%)): 527 [M]+
3
rel
+
(100), 345 [M – (MeO) C H NH] (26). Found (%): C, 68.35;
3
6
2
7
.15—7.55 (m, 11 H); 7.02 (t, 1 H, J = 4.3 Hz); 4.11 (s, 2 H).
H, 4.74; N, 2.72. C H NO S. Calculated (%): C, 68.30;
30 25 6
H, 4.78; N, 2.65.
1
3
C NMR (50.32 MHz, CDCl ), : 193.27, 176.30, 155.80,
3
1
55.71, 144.82, 135.51, 134.41, 133.29, 131.61, 131.57, 130.46
Reaction of bromo derivatives 7a,b,d with morpholine (general
procedure). A mixture of compound 7 (0.184 mmol) and morꢀ
pholine (0.036 g, 0.46 mmol) in DMF (3 mL) was stirred with
mild heating (T < 60 C) in the presence of K CO (25.4 mg,
(
1
2 C); 129.77 (2 C); 129.42 (2 C); 129.01 (2 C); 128.46, 127.35,
26.88, 126.03, 125.67, 123.22, 120.13, 118.03, 39.19. MS, m/z
+
+
(
Irel (%)): 454 [M] (3), 346 [M – C H S] (21), 317 [M –
6 5
2
3
+
+
+
–
5
C H S – COH] (14), 92 [C H O] (70), 91 [C H O] (100),
0.184 mmol). After the reaction reached completion (TLC moniꢀ
toring), the mixture was poured in water. A precipitate formed
was filtered off, washed with water, dissolved in dichloroꢀ
methane, and passed through a layer of silica gel. After evaporaꢀ
tion of the solvent, the residue was recrystallized from hexane.
2ꢀ(Furanꢀ2ꢀyl)ꢀ3ꢀ[(4ꢀmorpholinꢀ4ꢀylmethyl)benzoyl]ꢀ4Hꢀ
chromenꢀ4ꢀone (8e). The yield was 71%, m.p. 169—171 C.
6
5
6
4
6
3
+
5 [C S] (86). Found (%): C, 71.35; H, 4.03; S, 14.20. C H O S .
2 27 18 3 2
Calculated (%): with 71.34; H, 3.99; S, 14.11.
ꢀ(Furanꢀ2ꢀyl)ꢀ3ꢀ(4ꢀphenoxymethylbenzoyl)ꢀ4Hꢀchromenꢀ4ꢀ
one (8c). Bromo derivative 7a (0.075 g, 0.183 mmol) was added
to a mixture of K CO (0.026 g, 0.188 mmol) and phenol (0.018 g,
0
until the reaction reached completion (TLC monitoring). Then
the mixture was poured in water, a precipitate formed was filꢀ
tered off, washed with water, dissolved in dichloromethane, and
passed through a layer of silica gel, the solvent was evaporated.
2
2
3
.191 mmol) in DMF (3 mL), the mixture was stirred at T <70 C
1
H NMR (CDCl ), : 8.19 (d, 1 H, J = 7.9 Hz); 7.95 (d, 2 H,
3
J = 8.1 Hz); 7.72 (t, 1 H, J = 7.6 Hz); 7.56 (d, 1 H, J = 8.5 Hz);
7.38—7.49 (m, 4 H); 7.17 (d, 1 H, J = 3.5 Hz); 6.52 (t, 1 H,
J = 1.9 Hz); 3.68—3.78 (m, 4 H); 3.53 (s, 2 H); 2.48 (s, 4 H).
1
13
The yield was 51%, m.p. 168—170 C. H NMR (CDCl ), :
C NMR (50.32 MHz, CDCl ), : 192.29, 176.25, 155.80,
3
3
8
.21 (d, 1 H, J = 7.5 Hz); 8.02 (d, 2 H, J = 7.7 Hz); 7.74 (t, 1 H,
155.72, 151.39, 146.24, 145.28, 136.33, 134.39, 129.43 (4 C);
J = 7.4 Hz); 7.22—7.61 (m, 7 H); 7.16 (d, 1 H, J = 3.0 Hz);
125.98, 125.57, 123.47, 119.07, 117.95, 115.88, 112.46, 66.78
13
+
6
.89—7.03 (m, 3 H); 6.52 (s, 1 H); 5.12 (s, 2 H). C NMR
(2 C); 62.92, 53.58 (2 C). MS, m/z (I (%)): 415 [M] (54), 330
rel
+
+
(
50.32 MHz, CDCl ), : 192.26, 176.23, 158.47, 155.55, 151.42,
[M – C H NO] (100), 239 [M – C H – CH – C H NO]
4 8 6 4 2 4 8
(11), 146 [M – C H CH – C H NO – C H O] (21), 85
6 4 2 4 8 4 3
[C H NO] (41). Found (%): C, 72.33; H, 5.12; N, 3.35.
4 8
3
+
1
(
1
46.67, 145.23, 143.17, 136.65, 134.39, 129.63 (2 C); 129.58
2 C); 127.33 (2 C); 125.98, 125.58, 123.45, 121.24, 118.93, 117.95,
15.84, 114.82 (2 C); 112.48, 69.26. MS, m/z (I (%)): 422
+
C H NO . Calculated (%): C, 72.28; H, 5.10; N, 3.37.
25 21 5
rel
+
+
[
M] (8), 329 [M – C H O] (100), 119 (11), 95 (13), 73 (26).
3ꢀ[(4ꢀMorpholinꢀ4ꢀylmethyl)benzoyl]ꢀ2ꢀ(thiophenꢀ2ꢀyl)ꢀ4Hꢀ
chromenꢀ4ꢀone (9d). The yield was 61%, m.p. 157—159 C.
6
5
Found (%): C, 76.73; H, 4.34. C27H O . Calculated (%):
18
5
1
C, 76.77; H, 4.29.
H NMR (CDCl ), : 8.19 (d, 1 H, J = 7.8 Hz); 8.96 (d, 2 H,
3
Reaction of compounds 7a and 7b with 3,4,5ꢀtrimethoxyaniline
J = 8.0 Hz); 7.75 (t, 1 H, J = 7.5 Hz); 7.40—7.61 (m, 6 H); 7.02
(
3
general procedure). A mixture of compound 7 (0.184 mmol) and
,4,5ꢀtrimethoxyaniline (0.04 g, 0.221 mmol) in DMF (3 mL)
(t, 1 H, J = 4.4 Hz); 3.65—3.76 (m, 4 H); 3.52 (s, 2 H); 2.46
13
(s, 4 H). C NMR (75.47 MHz, CDCl ), : 193.45, 176.35,
3
was stirred with mild heating (T < 60 C) in the presence of
155.83, 155.72, 135.84, 134.49, 134.41, 133.37, 131.59, 131.51,
K CO (0.025 g, 0.184 mmol). After the reaction reached comꢀ
129.62 (4 C); 128.44, 126.10, 125.67, 123.24, 120.26, 118.03,
2
3
+
pletion (TLC monitoring), the mixture was poured in water.
A precipitate formed was filtered off, washed with water, disꢀ
solved in dichloromethane, and passed through a layer of silica
gel, the solvent was evaporated to give the product 8d or 9c.
66.88 (2 C); 62.96, 53.67 (2 C). MS, m/z (I (%)): 431 [M]
rel
+
+
(18), 346 [M – C H NO] (100), 317 [M – C H NO – CO] (14),
4
8
4
8
+
255 [M – C H CH – C H NO] (21), 146 [M – C H CH –
6
4
2
4
8
6
4
2
+
+
– C H NO – C H S] (23), 85 [C H NO] (30). Found (%):
4
8
4
3
4
8
2
ꢀ(Furanꢀ2ꢀyl)ꢀ3ꢀ{4ꢀ[(3,4,5ꢀtrimethoxyphenylamino)methꢀ
C, 69.54; H, 4.96; N, 3.21; S, 7.52. C H NO S. Calculatꢀ
25 21 4
yl]benzoyl}ꢀ4Hꢀchromenꢀ4ꢀone (8d). The yield was 48%, m.p.
ed (%): C, 69.59; H, 4.91; N, 3.25; S, 7.43.

1
768
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Semenova et al.
3
ꢀ[(5ꢀMorpholinꢀ4ꢀylmethyl)thiopheneꢀ2ꢀcarbonyl]ꢀ2ꢀ(thioꢀ
4. D. Yu, A. Brossi, N. Kilgore, C. Wild, G. Alloway, K. H.
Lee, Bioorg. Med. Chem. Lett., 2003, 13, 1575.
5. A. C. Gutierrez, M. H. Gehlen, Spectrochimica Acta, Part A,
2002, 58, 83.
phenꢀ2ꢀyl)ꢀ4Hꢀchromenꢀ4ꢀone (10). The yield was 54%, m.p.
98—200 C. H NMR (CDCl ), : 8.23 (d, 1 H, J = 5.8 Hz);
.74 (t, 1 H, J = 7.8 Hz); 7.56—7.63 (m, 3 H); 7.53 (d, 1 H,
1
1
7
3
J = 3.8 Hz); 7.45 (t, 1 H, J = 8.1 Hz); 7.07 (t, 1 H, J = 4.5 Hz);
6. M. M. Krayushkin, K. S. Levchenko, V. N. Yarovenko, L. V.
Christoforova, V. A. Barachevsky, Y. A. Puankov, T. M.
Valova, O. I. Kobeleva, K. Lyssenko, New J. Chem., 2009,
33, 2267.
7. A. S. Klymchenko, T. Ozturk, V. G. Pivovarenko, A. P.
Demchenko, Tetrahedron Lett., 2001, 42, 7967.
8. V. A. Barachevsky, Y. P. Strokach, Y. A. Puankov, O. I.
Kobeleva, T. M. Valova, K. S. Levchenko, V. N. Yarovenko,
M. M. Krayushkin, ARKIVOC, 2009, ix, 70.
6
.88 (d, 1 H, J = 3.8 Hz); 3.70—3.76 (m, 6 H); 2.51 (s, 4 H).
1
3
C NMR (75.47 MHz, CDCl ), : 185.16, 175.98, 155.92,
3
1
1
55.77, 154.03, 143.10, 134.97, 134.42, 133.36, 131.82, 131.66,
28.53, 126.93, 126.17, 125.72, 123.36, 120.13, 118.04, 67.01
(
[
(
2 C); 58.02, 53.61 (2 C). MS, m/z (I (%)): 437 [M]+ (9), 352
rel
+
+
M – C H NO] (82), 255 [M – C H SCH – C H NO]
100), 86 [C H NO] (38). Found (%): C, 66.21; H, 4.88;
4
8
4
3
2
4
8
+
4
8
N, 3.23; S, 14.79. C H NO S . Calculated (%): C, 66.18;
2
4
21
3 2
H, 4.86; N, 3.22; S, 14.72.
9. M. M. Krayushkin, K. S. Levchenko, V. N. Yarovenko, I. V.
Zavarzin, V. A. Barachevsky, Y. A. Puankov, T. M. Valova,
O. I. Kobeleva, ARKIVOC, 2009, ix, 269.
10. K. R. Huffman, C. E. Kuhn, A. Zweig, J. Am. Chem. Soc.,
1970, 92, 599.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 10ꢀ03ꢀ00250ꢀa)
and the Presidium of the Russian Academy of Sciences
1
1
1
1. R. T. Cummings, J. P. Dizio, G. A. Krafft, Tetrahedron Lett.,
988, 29, 69.
2. K. A. Thakar, V. N. Ingle, Ind. J. Chem., Sect., B, 1977, 15B,
059.
3. J. T. Ganvir, V. N. Ingle, J. Ind. Chem. Soc., 1988, 65, 878.
(
Program for Support of Innovation and Development).
1
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3
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2
Received August 10, 2012;
1
988, 10, 967.
in revised form October 5, 2012