New luminescent dyes from the series of 1,3,7-substituted dibenzothiophene-5,5-diones

Article abstract of DOI:10.1134/S1070428011110200

Preparation method was developed and a series of new linear polyconjugated compounds was obtained with (1,3-benzoxazol-2-yl)ethenyl, (5-oxo-2-phenyl-1,3- oxazolidine)methyl moieties in the positions 3, 7 of dibenzothiophene-5,5-dione frame and with peripheral alkoxy- and alkylamine substituents in the position 1. Compounds obtained possess a strong luminescence in solutions, in the solid state, and exhibit electroluminescent properties.

Full text of DOI:10.1134/S1070428011110200

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 11, pp. 1761−1766. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.K. Ol’khovik, V.G. Petushok, G.V. Kalechits, A.V. Baranovskii, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47,
No. 11, pp. 1722−1726.
New Luminescent Dyes from the Series of 1,3,7-Substituted
Dibenzothiophene-5,5-diones
V. K. Ol’khovika, V. G. Petushoka, G. V. Kalechitsa, and A. V. Baranovskiib
aInstitute of Chemistry of New Materials, National Academy of Sciences of Belarus’
Minsk, 220141 Belarus’
e-mail: slavol@ichnm.basnet.by
bInstitute of Bioorganic Chemistry, National Academy of Sciences of Belarus’, Minsk
Received February 23, 2011
Abstract—Preparation method was developed and a series of new linear polyconjugated compounds was obtained
with (1,3-benzoxazol-2-yl)ethenyl, (5-oxo-2-phenyl-1,3-oxazolidine)methyl moieties in the positions 3, 7 of
dibenzothiophene-5,5-dione frame and with peripheral alkoxy- and alkylamine substituents in the position 1.
Compounds obtained possess a strong luminescence in solutions, in the solid state, and exhibit electroluminescent
properties.
DOI: 10.1134/S1070428011110200
Linear polyconjugated organic compounds have
attracted high attention of researchers in the last decades
since they are connected with the new vigorously
developing technological field, molecular electronics.
Due to their structural versatility and a wide range of
specific optical, electrochemical, and electric properties
they are extensily utilized in designing new means of
information storage (ОLED) [1, 2], in production of
organic field transistors [3, 4], devices for transformation
of the solar energy [5], for storage and processing of
information [6] etc.
In extension of research on the investigation of
electroactive poly-π-conjugated compounds [7–10] we
report here on the results of the study of properties and
the synthesis of a series of new linear polyconjugated
compounds based on dibenzothiophene.
We investigated linear molecules with the 5,5-di-
oxodibenzothiophene core connected with chains of
conjugated electron-donor and electron-acceptor groups,
in particular, compounds containing in the conjugation
chain a 1,3-oxazole moiety. Due to the electron-deficient
nature of the oxazole moiety and of SO2 group of the
dibenzothiophene-5,5-dione fragment these compounds
should possess good electronic conductivity, and that is
very important in designing light-emitting diodes. Besides
the planar conformation of the dibenzothiophene ring
system governs the high π-conjugation along the total
molecular chain, and this permits the prediction in such
molecules of electroluminescent properties. We presumed
that the introduction of additional electron-donor groups
into the position 1 of the dibenzothiophene framework
would significantly affect the optical characteristics of
compounds synthesized and would make it possible to
obtain a series of efficient luminophores radiating in a
wide spectral range.
The procedure of the synthesis of initial 1-alkoxy-
or 1-amino-5,5-dioxodibenzothiophene-3,7-dicarb-
aldehydes II–VI from dimethyl biphenyl-4,4'-
dicarboxylate we have described before [7].
The introduction of 1,3-benzoxazol-2-ylethenyl
fragments into the molecule of dibenzothiophene-5,5-
dione was performed in one stage by the condensation
of dicarbaldehydes II–VI with a slight excess of
2-methylbenzoxazole (VII) in DMSO in the presence
of an equimolar quantity of sodium methylate as a base
(Scheme 1). As a result the most stable trans-trans-
isomers of 1-substituted 3,7-bis[2-(1,3-benzoxazol-2-yl)
ethenyl]dibenzothiophene-5,5-diones VIII–XII formed
in good yield(75–82%) and with high stereoselectivity.
The formation of the thermodynamically more stable
isomers was confirmed by the 1Н NMR data. The signals
of the ethenyl protons are split with large coupling
constants characteristic of the trans configuration.
1761

OL’KHOVIK et al.
1762
Scheme 1.
R
N
O
O
O
H
MeO2C
CO2Me
+
Me
S
H
O
O
I
VII
II_VI
NaOMe,DMSO
R
9
1
10'
8
2
10
11
N
O
N
7
3
11'
12'
O
6
4
12
13
S
13'
5
O
O
VIII_XII
R = OMe (II, VIII), OC6H13 (III, IX), N(Me)2 (IV, X), NHC4H9 (V, XI), NHC6H13 (VI, XII).
Scheme 2.
12'
11'
12
11
10
R
O
O
O
O
13'
14'
II_VI
13
14
10'
1
9
2
8
15'
O
7
3
N
N
15
O
Ac2O, Na2CO3
BzNHCH2COOH
6
4
S
N
5
O
O
XIII
XIV_XVIII
R = OMe (II, XIV), OC6H13 (III, XV), N(Me)2 (IV, XVI), NHC4H9 (V, XVII), NHC6H13 (VI, XVIII).
1-butylamino XVII derivatives. The detection was carried
out both by the absorption in the UV region and by the
ion current using mass detector. In the chromatogram
with the detection by ion current for both compounds
was found a single peak at the detection of positive as
well as negative ions.
The synthesis of derivatives containing methylidene-
1,3-oxazol-5-one fragments is presented in Scheme 2.
The attempt to obtain azalactones XIV–XVIII
under the conditions of the classic Erlenmeyer–Plächl
reaction from hippuric acid and dialdehydes II–VI in the
presence of sodium acetate in acetic anhydride provided
the target compounds in low yield, less than 30%. We
succeeded in notable increase in the yield when the
condensation reaction was carried out in two steps. The
reaction was started by heating hippuric acid and sodium
carbonate in acetic anhydride till complete dissolution.
Then to the solution of 2-phenyl-1,3-oxazol-5-one
(XIII) formed in the first stage were added dialdehydes
II–VI whose successive condensation to the activated
methylene group in oxazolone XIII furnished substituted
dibenzothiophenes XIV–XVIII in 60–82% yields.
The fragmentation of the corresponding ions
(MS2 experiment) revealed some peculiarities in
the fragmentation of the protonated molecules and
additionally confirmed the presence of a single isomer
corresponding to the main peak. The characteristic
feature of the fragmentation of protonated molecules of
compounds XV, XVII consists in a successive ejection
of carbon monoxide elements from the oxazolone ring
and in the elimination of the phenyl group.
The structure of compounds obtained was also
confirmed by the IR and 1Н NMR spectra. The IR spectra
of both groups of compounds VIII–XII and XIV–XVIII
contain strong absorption bands at 1575–1500 and
1560–1500 cm–1 characteristic of the bending vibrations
The stereoselectivity of the reaction was studied
applying HPLC method. The analysis of the homogeneity
of products was performed on 1-hexyloxy XV and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 11 2011

NEW LUMINESCENT DYES
1763
of the ring fragment –N=С–О–, very strong bands [1340–
1310, 1165–1150 (IV), 1355–1315, 1185–1155 cm–1] of
symmetric and antisymmetric vibrations of the О=S=О
group, and the bands of the stretching vibrations of СН
in the aromatic rings in the region 3110–3035 cm–1.
465 and 632 nm including all visible spectrum range
(see the table). As seen from the reported data the
introduction of the electron-donor alkylamine group
in the position 1 of the dibenzothiophene fragment
results in the shift of the luminescence maximum to the
longwave region and in the sharp growth of the value of
the Stokes shift which in the case of compound XVIII
reached abnormally large magnitude of 208 nm. Besides
amino derivatives X–XII, XVI–XVIII show a strong
solvatochromic effect, and on replacement of toluene by
highly polar dimethylformamide a red shift is observed
of the luminescence maximum (more than by 50 nm) and
a strong blue shift in the absorption spectra.
1
In the Н NMR spectra of 1-alkoxy and 1-alkylamino
derivatives VIII–XII, XIV–XVIII in the region 0.91–
4.45 ppm signals were observed belonging to the protons
of methyl and methylene groups of the alkyl moieties with
the characteristic multiplicity. The signals of NH protons
in the spectra of compounds appear as broadened singlets
in the region 5.85–6.40 ppm. The aromatic protons of
the dibenzothiophene-5,5-dione fragment appear in the
most downfield part of the spectrum (7.70–8.85 ppm), the
protons at С6,8,9 are clearly identified by the multiplicity of
the signals. The protons Н2,4 in the spectra of 1-alkylamino
derivatives X–XII, XVI–XVIII give rise to doublets with
small coupling constants (1–1.5 Hz) and apparently the
most upfield signal belongs to the proton Н2 owing to the
shielding effect of the amino group in the ortho-position.
The multiplets of the rest of the aromatic protons of the
2-phenyl-1,3-oxazolin-5-one and 1,3-benzoxazol-2-yl
fragments are located in the region 7.30–8.16 ppm.
The possibility to use alkoxy derivatives IX, XIV as
emitting layers in the organic light-emitting devices was
shown by an example of the electroluminescence material
of the structure ITO/NPB (60 nm)/IX (XIV)(20 nm)/TPBi
(10 nm)/Alq3 (30 nm)/LiF (1nm)/Al. The maximum elec-
troluminescence of these compounds is observed in the
more longwave region, at 544 and 540 nm respectively.
The electroluminescence properties of amino derivatives
are under study.
EXPERIMENTAL
All compounds synthesized VIII–XII, XIV–XVIII
possess a strong luminescence in solutions and in the
solid state. Depending on the nature of substituents
in the positions 1, 3, 7 of the dibenzothiophene
framework and on their combination the maximum of
the photoluminescence of the solution lies between
Melting points were measured on a Koeffler heat-
ing block equipped with an electronic thermometer
Hanna HI 93530. 1Н NMR spectra were registered from
DMSO-d6 solutions on spectrometers BrukerAvance-500
(500 MHz) and Tesla BS-587A(100 MHz) using TMS as
UV absorption and photoluminescence of compounds VIII–XII, XIV–XVII
Absorption, λmax, nm
Luminescence, λmax, nm
DMF
Compound no.
toluene
380, 430
379, 430
407, 437
399, 445
397, 456
469, 499
468, 499
458, 486
439, 506
440, 505
DMF
toluene
466
467
499
497
498
521
523
580
573
575
VIII
IX
390, 412
390, 411
362, 401
352, 434
344, 439
352, 415
344, 406
355, 402
358, 418
364, 424
465
466
549
546
547
524
519
614
627
632
X
XI
XII
XIV
XV
XVI
XVII
XVIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 11 2011

OL’KHOVIK et al.
1764
7.37 t (2H, H11,11'/H12,12', J 5.8 Hz), 7.42 t (2H, H11,11'
H12,12', J 7.0 Hz), 7.55 d (1H, =CH–, J 16.5 Hz), 7.65 d
(1H, =CH–, J 16.5 Hz), 7.72 d (2H, H10, H10,10'/H13,13'
J 8.0 Hz), 7.76 d (2H, H10,10'/H13,13', J 8.0 Hz), 7.83 с (1Н,
H2/H4/H6), 7.85 d (1H, =CH–, J 15.5 Hz), 7.86 d (1H,
=CH–, J 15.5 Hz), 8.07 s (1Н, H2/H4/H6), 8.11 d (1Н, H8/
H9, J 8.0 Hz), 8.23 d (1Н, H8/H9, J 8.0 Hz), 8.51 s (1Н,
H2/H4/H6). Mass spectrum, m/z: 603 [M + 1]+. M 602.
C36H30N2O5S. M 602.70.
/
internal reference. IR spectra were recorded on a spec-
trophotometer Specord M-80 from pellets with KBr.
UV spectra and fluorescence sperctra were obtained on
a spectrofluorimeter Solar CM2203 (cell thickness 1 cm).
Mass spectra (MS and MS2) were taken on an instrument
HPLC Acсela with a mass detector LCQ-Fleet (three-
dimension ion trap) in the chemical ionization mode at
the atmospheric pressure (APCI), detection of positive
and negative ions, CID 35%. HPLC conditions: column
Hypersil Gold (50 mm × 2.1 mm × 1.9 μm), mobil phase
95% MeCN (100 μl/min), the amount of the injected
probe 30 ng. The purification and drying of solvents
and reagents was carried out by common methods [11].
The reaction progress was monitored by TLC on plastic
plates with silica gel 60 A, F254 (Merck Art. 7734), elu-
ent toluene, development under UV irradiation at 254
and 365 nm.
,
3,7-Bis[(Е)-2-(1,3-benzoxazol-2-yl)ethenyl]-1-
(dimethylamino)-5H-dibenzo[b,d]thiophene-5,5-dione
(X). Yield 81%, mp 335–336°С. IR spectrum, cm–1: 3075,
3005, 2965, 2800, 1645, 1595, 1575, 1535, 1480, 1455,
1410, 1355, 1305, 1250, 1190, 1170, 1120, 1055, 1020,
980, 950, 900, 870, 840, 775, 755, 735. 1Н NMR spec-
trum, δ, ppm: 2.87 s (6Н, Me2N), 7.40 t (2Н, H11,11'/H12,12'
,
J 7.8 Hz), 7.43 t (2Н, H11,11'/H12,12', J 7.5 Hz), 7.60 d (1Н,
=CH–, J 16.0 Hz), 7.65 d (1Н, =CH–, J 16.0 Hz), 7.74 d
Compounds VIII–XII. General procedure. To a solu-
tion of 1 mmol of dialdehyde II–VI and 270 mg (2 mmol)
of 2-methyl-1,3-benzoxazol in 15 ml of anhydrous DMSO
was added at stirring a solution of 90 mg (2 mmol) of
MеОNa in 5 ml of methanol. The reaction mixture was
stirred for 16 h at 40–50°С. The precipitate was filtered
off, washed with water, 5% HCl, and again with water,
then it was recrystallized from DMSO.
(2Н, H10,10'/H13,13', J 7.5 Hz), 7.78 d (2Н, H10,10'/H13,13'
,
J 7.5 Hz), 7.90 s (1Н, H2/H4/H6), 7.92 d (2Н, CH=CH,
J 16.0 Hz), 8.17 s (1Н, H2/H4/H6), 8.18 d (1Н, H8/H9,
J 8.0 Hz), 8.33 d (1Н, H8/H9, J 8.0 Hz), 8.54 s (1Н,
H2/H4/H6). Mass spectrum, m/z: 546 [M + 1]+. M 545.
C32H23N3O4S. M 545.61.
3,7-Bis[(Е)-2-(1,3-benzoxazol-2-yl)ethenyl]-1-
(butylamino)-5H-dibenzo[b,d]thiophene-5,5-dione
(XI). Yield 82%, mp 327–329°С. IR spectrum, cm–1:
3415, 3075, 3035, 2975, 2940, 2880, 2865, 1635, 1590,
1570, 1545, 1490, 1470, 1450, 1440, 1420, 1350, 1290,
1235, 1215, 1185, 1157, 1150, 1115, 1080, 1065, 1005,
970, 945, 895, 880, 855, 835, 815, 760, 740, 715. 1Н NMR
spectrum, δ, ppm: 1.02 t (3Н, СН3, J 6.8 Hz), 1.54 m
(2Н, СН2), 1.78 m (2Н, NСН2СН2), 3.44 m (2Н, NСН2),
5.85 s (1Н, NH), 7.37–7.47 m (4Н, H11,11',12,12'), 7.43 d
(1Н, =CH–, J 17.0 Hz), 7.50 d (1Н, =CH–, J 17.0 Hz),
3,7-Bis[(Е)-2-(1,3-benzoxazol-2-yl)ethenyl]-1-
methoxy-5H-dibenzo[b,d]thiophene-5,5-dione (VIII).
Yield 91% (yellow crystals), mp >380°С. IR spectrum,
cm–1: 2945, 2870, 1650, 1600, 1595, 1540, 1465, 1420,
1365, 1320, 1260, 1175, 1065, 1025, 985, 955, 910,
1
875, 855, 780, 765, 735. H NMR spectrum, δ, ppm:
4.17 s (3Н, СН3О), 7.39 t (2H, H11,11'/H12,12', J 5.8 Hz),
7.42 t (2H, H11,11'/H12,12', J 7.0 Hz), 7.58 d (1H, =CH–,
J 16.5 Hz), 7.69 d (1H, =CH–, J 16.5 Hz), 7.74 d (2H,
H10,10'/H13,13', J 8.0 Hz), 7.77 d (2H, H10,10'/H13,13'
,
7.70 d (2H, H10,10'/H13,13', J 6.5 Hz), 7.75 d (2H, H10,10'
/
J 8.0 Hz), 7.89 s (1Н, H2/H4/H6), 7.92 d (1H, =CH–,
J 15.5 Hz), 7.94 d (1H, =CH–, J 15.5 Hz) 8.09 s (1Н,
H2/H4/H6), 8,15 d (1Н, H8/H9, J 8.0 Hz), 8.32 d (1Н, H8/
H9, J8.0 Hz), 8.51 s (1Н, H2/H4/H6). Mass spectrum, m/z:
533 [M + 1]+. M 532. C31H20N2O5S. M 532.57.
H13,13', J 6.5 Hz), 7.64 s (1Н, H2/H4/H6), 7.82 s (1Н, H2/
H4/H6), 7.90 d (1Н, =CH–, J 17.0 Hz), 7.94 d (1Н, =CH–,
J 17.0 Hz), 8.11 d (1Н, H8/H9, J 8.0 Hz), 8.27 d (1Н, H8/
H9, J 8.0 Hz), 8.37 с (1Н, H2/H4/H6). Mass spectrum,
m/z: 574 [M + 1]+. C34H27N3O4S. M 537.67.
3,7-Bis[(Е)-2-(1,3-benzoxazol-2-yl)ethenyl]-1-
hexyloxy-5H-dibenzo[b,d]thiophene-5,5-dione (IX).
Yield 88%, mp 269–271°С. IR spectrum, cm–1: 2940,
2870, 1640, 1595, 1575, 1535, 1455, 1415, 1355, 1310,
1245, 1190, 1165, 1045, 1015, 975, 945, 900, 865, 840,
3,7-Bis[(Е)-2-(1,3-benzoxazol-2-yl)ethenyl]-1-
(hexylamino)-5H-dibenzo[b,d]thiophene-5,5-dione
(XII). Yield 81%, mp 278–280°С. IR spectrum, cm–1:
3080, 2970, 2940, 2870, 1645, 1600, 1575,1530, 1475,
1455, 1420, 1355, 1305, 1245, 1185, 1160, 1120,1065,
1015, 975, 945, 900, 865, 830, 775, 755, 725. 1Н NMR
spectrum, δ, ppm: 0.90 t (3Н, СН3, J 6.8 Hz), 1.29–
1
775, 750, 730. Н NMR spectrum, δ, ppm: 0.91 t (3H,
CH3, J 7.0 Hz), 1.31–1.45 m (4H, CH2), 1.54 m (2H,
CH2), 1.93 m (2H, OCH2), 4.34 t (2H, OCH2, J 6.5 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 11 2011

NEW LUMINESCENT DYES
1765
J 1.5 Hz). Mass spectrum, m/z (Irel, %): 659 [M + 1]+
(100), 698 [M – 1 + MeCN]– (14), 658 [M]– (100), 573
[M – 1 – 3CO]+ (26), 525 [M – 2CO – Ph]– (21). Mass
spectrum MS2659; m/z (Irel, %): 631 [M + 1 – CO]+ (100),
575 [M + 1 – 3CO]+ (16), 526 [M + 1 – 2CO – Ph]+ (16).
M 658. C38H30N2O7S. M 658.72.
1.40 m (4Н, СН2), 1.46 m (2Н, СН2), 1.71 m (2Н, СН2),
3.15–3.55 m (2Н, NСН2), 6.20 t (1Н, NH, J 5.3 Hz),
7.40–7.44 m (4Н), 7.46 s (1Н, H2/H4), 7.62 d (1Н, =CH–,
J 16.5 Hz), 7.64 d (1Н, =CH–, J 16.5 Hz), 7.73–7.77 m
(4Н), 7.82 s (1Н, H2/H4), 7.93 d (1Н, =CH–, J 16.0 Hz),
7.95 d (1Н, =CH–, J 16.0 Hz), 8.18 d (1Н, Н8, J1 8.5,
J2 1.0 Hz), 8.27 d (1Н, Н9, J 8.5 Hz), 8.55 d (1Н, H6, J
1.0 Hz). Mass spectrum, m/z: 602 [M + 1]+. C36H31N3O4S.
M 601.71.
4,4'-[(1-Dimethylamino-5,5-dioxo-5H-dibenzo-
[b,d]thiophene-3,7-diyl)di(methylidene)]bis[2-
phenyl-oxazole-5(4Н)-one] (XVI). Yield 65%, mp
320°С (decomp.). IR spectrum, cm–1: 3450, 3115, 3070,
2905, 2945, 2875, 1810, 1665, 1605, 1550, 1480, 1445,
1410, 1380, 1335, 1300, 1235, 1195, 1155, 1120, 1085,
Compounds XIV–XVIII. General procedure.
A mixture of 2.0 mmol of benzoylaminoacetic acid
and 2.0 mmol of sodium carbonate in 15 ml of acetic
anhydride was boiled for 20 min. Then still at heating to
the solution was added an appropriate aldehyde II–VII.
Several minutes later the reaction mixture get orange or
red depending on aldehyde used. The reaction mixture
was stirred at 100–110°С over 5 h, then it was cooled and
poured on ice. The precipitated crystals were filtered off,
washed with water and hot ethanol, and recrystallized
from DMSO.
1
1050, 1000, 885, 870, 790, 770, 715. Н NMR spec-
trum, δ, ppm: 2.93 s (6Н, Me2N), 7.52 s (1H, CH=C),
7.53 s (1H, CH=C), 7.70 m (4Н), 7.78 t (1Н, H13/H13',
J 7.5 Hz), 7.78 t (1Н, H13/H13', J 7.5 Hz), 8.17 m (4Н),
8.48 d (1Н, H9, J 8.5 Hz), 8.51 s (1Н, H2/H4), 8.57 s
(1Н, H2/H4), 8.83 d.d (1Н, H8, J1 8.5, J2 1.5 Hz), 8.84 s
(1Н, H6, J 1.5 Hz). Mass spectrum, m/z: 602 [M + 1]+.
C34H23N3O6S. M 601.63.
4,4'-[(1-Methoxy-5,5-dioxo-5H-dibenzo[b,d]-
thiophene-3,7-diyl)di(methylidene)]bis[2-phenyl-
oxazole-5(4Н)-one] (XIV). Yield 80%, mp 345°С
(decomp). IR spectrum, cm–1: 3120, 3075, 2910, 1815,
1665, 1610, 1575, 1500, 1455, 1420, 1385, 1340, 1300,
1190, 1175, 1125, 1110, 1080, 1060, 1020, 1005, 930,
4,4'-[(1-Butylamino-5,5-dioxo-5H-dibenzo-[b,d]
thiophene-3,7-diyl)di(methylidene)]bis[2-phenyl-
oxazole-5(4Н)-one] (XVII). Yield 68%, mp 300°С
(decomp.). IR spectrum, cm–1: 3450, 3070, 2975, 2945,
2880, 1805, 1660, 1605, 1560, 1495, 1455, 1420, 1380,
1335, 1305, 1240, 1180, 1160, 1125, 1085, 1040, 1090,
990, 890, 790, 775, 710. 1Н NMR spectrum, δ, ppm: 1.0 t
(3Н, СН3, J7.0 Hz), 1.51 m (2Н, СН2), 1.78 m (2Н, СН2),
3.42 m (2Н, NСН2), 6.40 с (1Н, NH), 7.16 s (1H, CH=C),
7.24 s (1H, CH=C), 7.52 m (4Н), 7.76 t (1Н, H13/H13',
J 7.5 Hz), 7.77 t (1Н, H13/H13', J 7.5 Hz), 8.15 m (4Н),
8.17 d (1Н, H9, J 8.5 Hz), 8.30 s (1Н, H2/H4), 8.41 s (1Н,
H2/H4), 8.71 d.d (1Н, H8, J1 8.5, J2 1.5 Hz), 8.82 s (1Н,
H6, J 1.5 Hz). Mass spectrum m/z (Irel, %): 630 [M + 1]+
(100), 628 [M – 1]– (100), 496 [M – 2CO – Ph]– (20). Mass
spectrum MS2630; m/z (Irel, %): 612 [M + 1 – H2O]+ (12),
602 [M + 1 – CO]+ (100), 574 [M + 1 – 2CO]+ (67), 497
[M + 1–2CO–Ph]+ (16). M 629. C36H27N3O6S. M 629.69.
1
895, 880, 860, 790, 775, 720. Н NMR spectrum, δ,
ppm: 4.23 s (3Н, СН3О), 7.50 s (1Н, СН=С), 7.51 s (1Н,
СН=С), 7.68 m (4Н), 7.772 t (1Н, H13/H13' J 7.0 Hz),
7.776 t (1Н, H13/H13', J 7.0 Hz), 8.17 m (4Н), 8.43 s (1H,
H2/H4), 8.46 s (1H, H2/H4), 8.52 d (1H, H9, J 8.5 Hz),
8.69 d.d (1Н, H8, J1 8.5, J2 1.5 Hz), 8.83 d (1Н, H6,
J 1.5 Hz). Mass spectrum, m/z: 589 [M + 1]+. M 588.
C33H20N2O7S. M 588.59.
4,4'-[(1-Hexyloxy-5,5-dioxo-5H-dibenzo[b,d]-
thiophene-3,7-diyl)di(methylidene)]bis[2-phenyl-
oxazole-5(4Н)-one] (XV). Yield 82%, mp 280°С
(decomp.). IR spectrum, cm–1: 3120, 3075, 2910, 2940,
2875, 1800, 1660, 1605, 1560, 1490, 1455, 1420, 1380,
1330, 1300, 1235, 1190, 1170, 1155, 1125, 1080, 1050,
4,4'-[(1-Hexylamino-5,5-dioxo-5H-dibenzo-[b,d]
thiophene-3,7-diyl)di(methylidene)]bis[2-phenyl-
oxazole-5(4Н)-one] (XVIII). Yield 66%, mp 290°С
(decomp.). IR spectrum, cm–1: 3445, 3050, 2965, 2940,
2880, 1805, 1665, 1605, 1565, 1495, 1455, 1415, 1370,
1330, 1305, 1240, 1175, 1160, 1120, 1085, 1040, 1080,
1
1000 895, 870, 790, 775, 710. Н NMR spectrum, δ,
ppm: 0.93 t (3Н, СН3, J 7.0 Hz), 1.36–1.44 m (4Н, СН2),
1.55–1.64 m (2Н, СН2), 1.98–2.04 m (2Н, СН2), 4.45 t
(2Н, ОСН2, J 6.5 Hz), 7.48 s (1H, CH=C), 7.50 s (1H,
CH=C), 7.68 m (4Н), 7.77 t (1Н, H13/H13', J 7.0 Hz),
7.78 t (1Н, H H13/H13', J 7.5 Hz), 8.16 m (4Н), 8.42 s (1Н,
H2/H4), 8.44 s (1Н, H2/H4), 8.47 d (1Н, H9, J 8.5 Hz),
8.65 d.d (1Н, H8, J1 8.5, J2 1.5 Hz), 8.83 d (1Н, H6,
1
995, 890, 785, 775, 715. Н NMR spectrum, δ, ppm:
0.88 t (3Н, СН3, J 7.0 Hz), 1.34 m (4Н, СН2), 1.48 m
(2Н, СН2), 1.79 m (2Н, СН2), 3.35 m (2Н, NСН2), 6.34 s
(1Н, NH), 7.47 s (1H, CH=C), 7.50 s (1H, CH=C), 7.67 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 11 2011

OL’KHOVIK et al.
1766
(4Н), 7.75 t (1Н, H13/H13', J 7.5 Hz), 7.77 t (1Н, H13/H13',
J 7.5 Hz), 8.13 m (4Н), 8.16 d (1Н, H9, J 8.5 Hz), 8.39
s (1Н, H2/H4), 8.67 s (1Н, H2/H4), 8.83 d.d (1Н, H8, J1
8.5, J2 1.5 Hz), 8.84 s (1Н, H6, J 1.5 Hz). Mass spectrum,
m/z: 658 [M + 1]+. C38H31N3O6S. M 657.74.
vol. 18, p. 2903.
6. Matsuoka, M., J. Soc.Dyers, Colour, 1989, vol. 105, p. 167.
7. Olkhovik,V.K.,Vasilevskii,D.A.,Pap,A.A.,Kalechyts,G.V.,
Matveienko, Y.V., Baran, A.G., Halinouski, N.A., and
Petushok, V.G., ARKIVOC., 2008, vol. IX, p. 69.
8. Ol’khovik, V.K., Pap, A.A., Vasilevskii, V.A.,
Galinovskii, N.A., and Tereshko, S.N., Zh. Org. Khim.,
2008, vol. 44, p. 1185.
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