Reaction of 8-arenesulfonyloxy-2-methylquinolines with 4,6-di(tert-butyl)-3-nitro-1,2-benzoquinone

Full text of DOI:10.1134/S1070428015040235

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 4, pp. 595–598. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © I.E. Mikhailov, A.A. Kolodina, Yu.M. Artyushkina, G.A. Dushenko, Yu.A. Sayapin, V.I. Minkin, 2015, published in Zhurnal
Organicheskoi Khimii, 2015, Vol. 51, No. 4, pp. 611–614.
SHORT
COMMUNICATIONS
Reaction of 8-Arenesulfonyloxy-2-methylquinolines
with 4,6-Di(tert-Butyl)-3-nitro-1,2-benzoquinone
I. E. Mikhailova, b, A. A. Kolodinaa, Yu. M. Artyushkinaa, b, G. A. Dushenkoa, c,
Yu. A. Sayapina, and V. I. Minkinc
a Southern Scientific Center, Russian Academy of Sciences, ul. Chekhova 41, Rostov-on-Don, 344006 Russia
e-mail: mikhail@ipoc.rsu.ru
b Southern Federal University, Bol’shaya Sadovaya ul. 105/42, Rostov-on-Don, 344006 Russia
c Institute of Physical and Organic Chemistry, Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090, Russia
Received November 19, 2014
DOI: 10.1134/S1070428015040235
Bidentate heterocyclic ligand systems with an =N-
(O-phenol) chelating fragment are widely used in the
synthesis of highly efficient organic [1, 2] and metal-
complex luminophors [3–5], as well as of electron
transport materials for organic light-emitting diodes
(OLEDs). Among the latter, a particular place is occu-
pied by 8-hydroxyquinoline and its derivatives [6].
High structural variability of the 8-hydroxyquinoline
system makes it possible to create new photo- and
electroluminescent materials with high operational and
performance characteristics [7]. Therefore, purposeful
modification of 8-hydroxyquinoline derivatives with
a view of obtaining new substances with practically
useful properties is a topical problem.
2-(4,6-di-tert-butyl-3-nitro-2,7-dioxocyclohepta-3,5-
dienylidene)-1,2-dihydroquinolin-8-yl arenesulfonates
3a and 3b, as well as their analogs having no nitro
group in the seven-membered ring, 2-(3,5-di-tert-
butyl-2,7-dioxocyclohepta-3,5-dienylidene)-1,2-dihy-
droquinolin-8-yl arenesulfonates 4a and 4b.
The low yields of expected compounds 3a and 3b
(14, 16%) and anomalous products 4a and 4b (8, 10%)
may be rationalized by the complex mechanism of the
reaction of 2-methylquinolines with 1,2-benzoqui-
nones [8, 9]. It should be noted that analogous acid-
catalyzed reaction of 1,2-benzoquinone 2 with 2-meth-
yl-8-hydroxyquinoline leads exclusively to tarry prod-
ucts, and ring expansion of the 1,2-benzoquinone
fragment with simultaneous introduction of tropolone
ring into position 2 of quinoline becomes possible only
when the hydroxy group is protected by an arenesul-
fonyl group.
With the goal of extending the series of such
8-hydroxyquinoline compounds, we have introduced
a 1,3-tropolone fragment into the 2-position of
8-arenesulfonyloxyquinoline via reaction of 2-methyl-
quinolines with 1,2-benzoquinones, which was report-
ed by us previously [8]. The reaction of 8-arenesul-
fonyloxy-2-methylquinolines 1a and 1b with 4,6-di-
(tert-butyl)-3-nitro-1,2-benzoquinone (2) gave
Obviously, compounds 3a, 3b, 4a, and 4b exist as
NH tautomers in which the NH proton is involved in
strong intramolecular hydrogen bond with one car-
bonyl group of the tropone fragment. This follows
Bu-t
O
O
Bu-t
Bu-t
AcOH
O
65°C, 30 h
N
N
+
+
H
H
OR
OR
N
Me
O
O
O
Bu-t
OR
Bu-t
Bu-t
NO2
O2N
3a, 3b
1a, 1b
2
4a, 4b
R = PhSO2 (a), 4-FC6H4SO2 (b).
595

MIKHAILOV et al.
596
from very strong downfield shift of the NH signal in
the H NMR spectra (δ 18.17–18.34 ppm) and upfield
2-Methylquinolin-8-yl 4-fluorobenzenesulfonate
(1b). Yield 4.27 g (90%), colorless crystals, mp 149–
150°C. IR spectrum, ν, cm–1: 1646 (C=N), 1607, 1582,
1576, 1377 (SO2), 1330, 1281, 1189 (SO2). H NMR
spectrum, δ, ppm: 2.52 s (3H, CH3), 7.08 d.d (2H,
1
shift of one carbonyl carbon signal by 19.6–22.1 ppm
relative to the other C=O signal in the 13C NMR
spectra. Furthermore, the spectral parameters of 3a,
3b, 4a, and 4b were similar to those of structurally
related compounds whose structure was determined by
X-ray analysis [8, 9].
1
H
arom, J = 8.5, 8.8 Hz), 7.20 d (1H, Hquin, J = 8.5 Hz),
7.44 d.d (1H, Hquin, J = 7.7, 7.9 Hz), 7.64–7.70 m (2H,
quin), 7.94–8.01 m (3H, Hquin, Harom). 13C NMR spec-
trum, δC, ppm: 25.7 (CH3), 116.2 d (2C, Carom, JCF
H
=
Taking into account that arenesulfonate protection
can readily be removed by alkaline hydrolysis, com-
pounds 3a, 3b, 4a, and 4b may be regarded as pre-
cursors of multidentate 8-hydroxyquinoline ligand
systems with a tropolone fragment in position 2 of the
quinoline ring. They also attract interest from the
viewpoint of preparation of new metal-complex lumi-
nophors for OLEDs [6] and biologically active com-
pounds, since both tropolone and its closest structural
analogs [10], as well as 8-hydroxyquinoline deriva-
tives [11], are known to exhibit a broad spectrum of
biological activity.
22.7 Hz), 123.2, 123.8, 125.6, 127.4, 128.3, 132.2 d
(2C, Carom, JCF = 9.7 Hz), 132.8 d (Carom, JCF = 3.1 Hz),
136.2, 141.1, 145.2, 160.1, 166.2 d (Carom, JCF
=
256.7 Hz). Mass spectrum, m/z (Irel, %): 317 (6) [M]+,
253 (49), 158 (65), 130 (100), 103 (25), 95 (20), 77
(24), 51 (9). Found, %: C 60.65; H 3.74; N 4.53.
C16H12FNO3S. Calculated, %: C 60.56; H 3.81; N 4.41.
Compounds 3a, 3b, 4a, and 4b (general proce-
dure). A mixture of 0.005 mol of quinoline 1a or 1b,
2.64 g (0.010 mol) of 4,6-di-tert-butyl-3-nitro-1,2-ben-
zoquinone (2) [13], and 5 mL of acetic acid was heated
for 30 h at 65–67°C. When the reaction was complete
(TLC), the mixture was diluted with cold water
(250 mL) and extracted with methylene chloride
(3×30 mL). The combined extracts were dried over
Na2SO4, the solvent was distilled off, and the residue
was subjected to alumina column chromatography
using petroleum ether–methylene chloride (1:1) as
eluent to isolate a fraction with Rf 0.50–0.65 (mixture
of compounds 3 and 4). The products were separated
by repeated column chromatography on silica gel
(ethyl acetate–petroleum ether, 1:3).
Thus, we have found that the presence of a free
hydroxy group in 2-methyl-8-hydroxyquinoline ham-
pers formation of tropolone ring in the reaction with
4,6-di(tert-butyl)-3-nitro-1,2-benzoquinone (2). Ex-
pansion of the quinone ring in 2 is observed only in
reactions with 2-methylquinoline derivatives in which
the 8-hydroxy group is protected by an arenesulfonyl
moiety, and the reaction is accompanied by partial
elimination of the nitro group.
2-Methylquinolin-8-yl arenesulfonates 1a and 1b
(general procedure). A solution of 0.018 mol of ben-
zene- or 4-fluorobenzenesulfonyl chloride in 10 mL of
benzene was added dropwise under stirring to a mix-
ture of 2.39 g (0.015 mol) of 2-methylquinolin-8-ol
and 3.5 mL of triethylamine in 20 mL of benzene. The
mixture was stirred for 1 h at room temperature and
heated for 0.5–1 h at 100°C, and the solvent was
distilled off. The oily residue was treated with 50 g of
crushed ice, and the precipitate was filtered off,
washed with cold water (2×30 mL), dried in air, and
recrystallized twice from ethanol.
2-(4,6-Di-tert-butyl-3-nitro-2,7-dioxocyclohepta-
3,5-dienylidene)-1,2-dihydroquinolin-8-yl benzene-
sulfonate (3a). Yield 0.385 g (14%), yellow crystals,
mp 232–233°C (from propan-2-ol), Rf 0.28 (EtOAc–
petroleum ether, 1:3). IR spectrum, ν, cm–1: 3115–
3020 (N–H), 1640 (C=O), 1618 (C=O), 1604, 1560,
1545 (NO2), 1495, 1459, 1390, 1353 (SO2), 1338,
1
1322 (NO2), 1227, 1318, 1188 (SO2). H NMR spec-
trum, δ, ppm: 1.25 s and 1.29 s (9H each, t-Bu), 6.34 s
(1H, 5′-H), 7.49 d.d (1H, Hquin, J = 7.4, 7.5 Hz), 7.56–
7.73 m (4H, Hquin, Harom), 7.92 d (1H, Hquin, J =
7.5 Hz), 8.03–8.13 m (2H, Hquin), 8.16–8.19 m (2H,
Harom), 18.17 s (1H, NH). 13C NMR spectrum, δC, ppm:
29.5 and 30.8 [C(CH3)3], 37.7 and 38.4 [C(CH3)3],
115.0, 119.6, 120.8, 125.4, 126.4 (2C), 129.7 (4C),
131.0, 134.5, 135.6 (2C), 138.5, 139.1, 143.3, 150.8,
153.0, 154.5, 175.1 and 194.8 (C=O). Mass spectrum,
m/z (Irel, %): 561 (7) [M – 1]+, 534 (11) [M – CO]+, 533
(30), 516 (31) [M – NO2]+, 492 (11), 461 (8), 375 (43),
332 (26), 304 (16), 290 (24), 185 (14), 141 (21), 75
2-Methylquinolin-8-yl benzenesulfonate (1a).
Yield 4.07 g (91%), colorless crystals, mp 113–114°C;
published data [12]: mp 109–110°C. IR spectrum, ν,
cm–1: 1605 (C=N), 1585, 1562, 1502, 1377 (SO2),
1
1332, 1312, 1187 (SO2). H NMR spectrum, δ, ppm:
2.48 s (3H, CH3), 7.18 d (1H, Hquin, J = 8.5 Hz), 7.37–
7.46 m (3H, Hquin), 7.54 d.d (1H, Harom, J = 7.3,
7.6 Hz), 7.61–7.69 m (2H, Harom), 7.92–7.99 m (3H,
Hquin, Harom).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 4 2015

REACTION OF 8-ARENESULFONYLOXY-2-METHYLQUINOLINES
597
(100), 57 (43). Found, %: C 64.09; H 5.32; N 5.03.
C30H30N2O7S. Calculated, %: C 64.04; H 5.37; N 4.98.
8.06 m (3H, Harom, Hquin), 8.10 d (1H, Hquin, J =
9.2 Hz), 18.25 s (1H, NH). 13C NMR spectrum,
δC, ppm: 30.4 and 31.5 [C(CH3)3], 37.6 and 38.7
[C(CH3)3], 115.4, 116.7 d (2C, Carom, JCF = 22.9 Hz),
121.7, 123.6, 123.8, 124.9, 125.8, 126.8, 127.5,
2-(4,6-Di-tert-butyl-3-nitro-2,7-dioxocyclohepta-
3,5-dienylidene)-1,2-dihydroquinolin-8-yl 4-fluoro-
benzenesulfonate (3b). Yield 0.465 g (16%), yellow
crystals, mp 253–254°C (from EtOH), Rf 0.10
(EtOAc–petroleum ether, 1:3). IR spectrum, ν, cm–1:
3118–3022 (NH), 1634 (C=O), 1618 (C=O), 1603,
1592, 1588, 1564, 1547 (NO2), 1501, 1480, 1438,
1403, 1359 (SO2), 1340, 1320 (NO2), 1281, 1234,
131.6 d (Carom, JCF = 3.2 Hz) 132.3 d (2C, Carom, JCF
=
9.8 Hz), 135.6, 137.3, 142.0, 154.8, 155.8, 157.2,
167.1 d (Carom, JCF = 289.8 Hz), 173.1 and 195.2
(C=O). Mass spectrum, m/z (Irel, %): 535 (4) [M]+, 507
(12) [M – CO]+, 492 (5), 349 (8), 332 (18), 318 (20),
292 (17), 276 (7), 248 (5), 159 (21), 91 (100), 75 (24),
57 (30), 41 (17). Found, %: C 67.33; H 5.54; N 2.51.
C30H30FNO5S. Calculated, %: C 67.27; H 5.65; N 2.61.
1
1189 (SO2). H NMR spectrum, δ, ppm: 1.30 s and
1.34 s (9H each, t-Bu), 6.40 s (1H, 5′-H), 7.34 d.d (2H,
Harom, J = 8.9, 9.1 Hz), 7.55 d.d (1H, Hquin, J = 7.8,
7.9 Hz), 7.73 d.d (1H, Hquin, J = 1.3, 7.9 Hz), 7.96 d.d
(1H, Hquin, J = 1.3, 7.9 Hz), 8.12 d (1H, Hquin, J =
9.2 Hz), 8.18 d (1H, Hquin, J = 9.2 Hz), 8.26–8.32 m
(2H, Harom), 18.34 s (1H, NH). 13C NMR spectrum,
δC, ppm: 29.5 and 30.82 [C(CH3)3], 37.8 and 38.4
[C(CH3)3], 115.0, 117.2 d (2C, Carom, JCF = 23.3 Hz),
The IR spectra were recorded on a Varian Excalibur
1
3100 FT-IR spectrometer from thin films. The H and
13C NMR spectra were measured on a Bruker DPX-
250 spectrometer at 250.13 and 62.90 MHz, respec-
tively, using CDCl3 as solvent and reference. The mass
spectra (electron impact, 70 eV) were obtained on
a Finnigan MAT INCOS 50 instrument. The elemental
analyses were obtained on a KOVO CHN analyzer.
Alumina (Brockmann activity grade II or III) and
Silica gel 60 (0.063–0.200 mm) were used for column
chromatography. The melting points were determined
on a Boetius hot stage.
119.7, 120.9, 125.5 (2C), 126.4, 126.5, 130.4 d (Carom
,
JCF = 3.5 Hz), 131.0, 132.9 d (2C, Carom, JCF
=
10.1 Hz), 138.4, 139.2, 143.5, 150.8, 153.1, 154.5,
167.2 d (Carom, JCF = 258.9 Hz), 175.0 and 194.6
(C=O). Mass spectrum, m/z (Irel, %): 579 (6) [M – 1]+,
552 (9) [M – CO]+, 551 (31), 534 [M – NO2]+ (11), 533
(27), 510 (8), 479 (6), 375 (37), 332 (24), 304 (15),
290 (23), 185 (17), 159 (48), 95 (100), 75 (24), 57 (74).
Found, %: C 62.23; H 5.14; N 4.75. C30H29FN2O7S.
Calculated, %: C 62.06; H 5.03; N 4.82.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (state contract no. 4.129.2014/K).
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mp 174–176°C (from propan-2-ol); published data [8]:
mp 174–176°C; Rf 0.49 (EtOAc–petroleum ether, 1:3).
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1
The H and 13C NMR, IR, and mass spectra and
elemental composition of the product coincided with
the data reported in [8].
2-(3,5-Di-tert-butyl-2,7-dioxocyclohepta-3,5-di-
enylidene)-1,2-dihydroquinolin-8-yl 4-fluoroben-
zenesulfonate (4b). Yield 0.214 g (8%), yellow
crystals, mp 163–164°C (from propan-2-ol), Rf 0.25
(EtOAc–petroleum ether, 1:3). IR spectrum, ν, cm–1:
3110–3032 (NH), 1638 (C=O), 1621 (C=O), 1602,
1591, 1563, 1496, 1480, 1461, 1439, 1407, 1358
1
(SO2), 1341, 1301, 1287, 1236, 1187 (SO2). H NMR
spectrum (CDCl3), δ, ppm: 1.27 s and 1.36 s (9H each,
t-Bu), 6.72 d and 6.78 d (1H each, 4′-H, 6′-H, J =
1.9 Hz), 7.12 d.d (2H, Harom, J = 9.1, 9.2 Hz), 7.44 d.d
(1H, Hquin, J = 7.8, 7.9 Hz), 7.61 d.d (1H, Hquin, J = 1.3,
7.9 Hz), 7.67 d.d (1H, Hquin, J = 7.9, 1.3 Hz), 7.99–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 4 2015

MIKHAILOV et al.
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