Simple synthesis of 3-hydroxyquinolines via Na2S2O4-mediated reductive cyclization of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones (o-nitrobenzalacetophenone oxides)

Article abstract of DOI:10.1016/j.tet.2017.06.058

An efficient sodium dithionite (Na₂S₂O₄)-mediated method for construction of 3-hydroxyquinolines via in situ Meinwald rearrangement/intramolecular reductive cyclization of o-nitrobenzalacetophenone oxides has been developed. The practical approach is of excellent functional group compatibility with as high as 98% yield under mild reaction conditions. Moreover, further manipulation successfully furnished 4-bromo substituted derivatives which may provide a promising potential application in exploring biologically active analogs of 3-hydroxyquinolines.

Full text of DOI:10.1016/j.tet.2017.06.058

Accepted Manuscript
Simple synthesis of 3-hydroxyquinolines via Na S O -mediated reductive cyclization
2 2 4
of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones (o-nitrobenzalacetophenone oxides)
Vakhid A. Mamedov, Vera L. Mamedova, Victor V. Syakaev, Dmitry E. Korshin,
Gul'naz Z. Khikmatova, Ekaterina V. Mironova, Olga B. Bazanova, Il'dar Kh.
Rizvanov, Shamil K. Latypov
PII:
S0040-4020(17)30701-9
10.1016/j.tet.2017.06.058
TET 28823
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 11 April 2017
Revised Date: 11 June 2017
Accepted Date: 27 June 2017
Please cite this article as: Mamedov VA, Mamedova VL, Syakaev VV, Korshin DE, Khikmatova Gul'Z,
Mironova EV, Bazanova OB, Rizvanov Il'Kh, Latypov SK, Simple synthesis of 3-hydroxyquinolines
via Na S O -mediated reductive cyclization of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones (o-
2 2 4
nitrobenzalacetophenone oxides), Tetrahedron (2017), doi: 10.1016/j.tet.2017.06.058.
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ACCEPTED MANUSCRIPT
Graphical abstract
Simple synthesis of 3-hydroxyquinolines via Na2S2O4-mediated reductive cyclization
of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones
(o-nitrobenzalacetophenone oxides)
Vakhid A. Mamedov*, Vera L. Mamedova, Victor V. Syakaev, Dmitry E. Korshin,
Gul’naz Z. Khikmatova, Ekaterina V. Mironova, Olga B. Bazanova,
Il’dar Kh. Rizvanov, Shamil K. Latypov

ACCEPTED MANUSCRIPT
Dedicated to the 80th anniversary of
Professor John A. Joule
Simple synthesis of 3-hydroxyquinolines via Na2S2O4-mediated reductive
cyclization of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones
(o-nitrobenzalacetophenone oxides)
Vakhid A. Mamedov*, Vera L. Mamedova, Victor V. Syakaev, Dmitry E. Korshin,
Gul’naz Z. Khikmatova, Ekaterina V. Mironova, Olga B. Bazanova,
Il’dar Kh. Rizvanov, Shamil K. Latypov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian
Academy of Sciences, Arbuzov str. 8, 420088 Kazan, Russian Federation
mamedov@iopc.ru
ABSTRACT: An efficient sodium dithionite (Na2S2O4)-mediated method for construction of 3-
hydroxyquinolines via in situ Meinwald rearrangement/intramolecular reductive cyclization of o-
nitrobenzalacetophenone oxides has been developed. The practical approach is of excellent
functional group compatibility with as high as 98% yield under mild reaction conditions. Moreover,
further manipulation successfully furnished 4-bromo substituted derivatives which may provide a
promising potential application in exploring biologically active analogs of 3-hydroxyquinolines.
Keywords:
Synthetic methods
Nitrogen heterocycles
trans-(2-(2-Nitrophenyl)oxiran-1-yl)(aryl)methanones
Reductive cyclization
Ring formation
3-Hydroxy-2-arylquinolines
4-Bromo-3-hydroxy-2-arylquinolines
1. Introduction
Quinolines are widely found in natural products1 and broadly used in medicinal chemistry2
among them, 3-hydroxyquinolines (quinolin-3-ols) are of extreme importance. For example,
naturally occurring viridicatin, viridicatol, and 3-O-methylviridicatin, compounds containing the 3-
hydroxyquinolin-2(1H)-one skeleton, are fungal metabolites isolated from penicillium species,
which have been reported to inhibit the replication of human immunodeficiency virus (HIV).3
Moreover, 3-hydroxyquinolines have also been intensively studied as antiallergenic agents, i.e. TA-
270,4 selective inhibitors of HIV-1 reverse transcriptase,5 potent D-amino acid oxidase (DAAO)
inhibitors,6 and maxi-K channel openers with antibacterial activities.7 Furthermore, quinolines were
used as building blocks to prepare functional materials with enhanced physical properties.8
Although the significance of this class of compounds is obvious, the synthesis of 3-
hydroxyquinoline derivatives has surprisingly, remained largely unexplored. Only a few methods
have been reported, including the condensation of aryldiazomethanes with isatins,9 transformation of
cyclopenin,10 Friedlander type condensations,11-13 Pfitzinger synthesis,14 Pd-catalyzed coupling
reactions,15 Knoevenagel condensation/epoxidation of cyanoacetanilides with aldehydes followed by
decyanative epoxide-arene cyclization sequence16 and Danheiser type benzannulation of 2-
iodostyrenes with tert-butoxyacetylene.17

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Unfortunately, these strategies, suffer from the disadvantages that the starting materials are only
available in limited supply and that the process of varying the substituents at positions 2 and 4 of 3-
hydroxyquinolines is cumbersome and lengthy. The main limitation of these methods is the
impossibility of their use in the synthesis of 3-hydroxyquinolin-2(1H)-one derivatives with no
substituent in position 4. Such derivatives are very important for the synthesis of parent 3-
hydroxyquinolines to which various substituents can then be introduced in this position. The
development of a novel method for the synthesis of derivatives 2 with complete control over both
positions 2 and 4 would therefore be of significant value.
Herein, we report a method developed for the convenient synthesis of the 3-hydroxyquinolines 2
with no substituent at position 4 starting from the readily available (2-(2-nitrophenyl)oxiran-1-
yl)(aryl)methanones 1. In a one-pot manner, the reactions proceed through a sodium dithionite
(Na2S2O4)-mediated reduction with a final intramolecular annulation step.
2. Results and discussion
The reaction of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones 1а-h with Na2S2O4 in boiling
water-dioxane medium proceeds with the formation of 3-hydroxy-2-arylquinolines 2а-h (Table 1) as
a result of 6-exo-trig cyclization18 with the participation of the amino group, formed as a result of the
reduction of the nitro group, and the carbonyl group of an aroyl fragment (Scheme 1). Although it
might be expected that the ortho-location of the epoxy ring relative to the nitro group in the
compounds 1а-h creates favorable conditions for the 5-exo-trig cyclization (Scheme 1), implemented
as a result of the attack of the amino group on the C1 atom of the epoxy ring, prone to ring-opening
with the formation of a dihydroindole derivative, the dehydration of which would provide indoles
2′а-h. Compounds 2а-h and 2′а-h have the same molecular weight and are hard to distinguish
without special NMR experiments. However, a detailed NMR spectroscopy study has allowed the
assignment of the obtained compounds to be structures 2а-h.
Table 1. Synthesis of 3-hydroxy-2-arylquinolines.
Entry
R
H
Ar
Product
2a
Yield,a %
1
1
2
3
4
5
6
7
8
Ph
92
93
98
89
85
91
91
98
1a
1b
1c
1d
1e
1f
Cl
H
Ph
2b
4-ClC6H4
4-ClC6H4
2-BrC6H4
4-MeC6H4
4-MeC6H4
4-MeOC6H4
2c
Cl
H
2d
2e
H
2f
Cl
1g
1h
2g
H
2h
aYields refer to isolated products.

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Scheme 1. Plausible pathways to 3-hydroxyquinolines 2a-h.
1
13
15
The complete assignment of the signals in the H, C and N NMR spectra was accomplished
using 2D NMR techniques (COSY, HSQC, HMBC). In this case we consider the example of
compound 2g. It is immediately obvious that several facts are inconsistent with the structure 2′g i.e. a
very small (150.2 ppm) chemical shift (CS) for the aroyl carbonyl carbon, the absence of cross peaks
in the HSQC (1H-15N) spectra, suggesting the absence of the NH group. However, we observe a
broadened peak with CS 10.72 ppm in the spectrum, which has a cross peak in the HMBC (1H-13C)
for the carbon with CS 150.3 ppm, which suggests the presence of group =С–ОН in the compound
1
studied. These facts suggest structure 2g. The assignment of signals in the H NMR spectrum is not
difficult (see Experimental section) and is consistent with the cross peaks in the COSY spectrum.
Assignment of the doublet with CS 7.92 ppm (J = 8.9 Hz) to H8 is confirmed by the cross peak in
HMBC (1Н-15N) with N1 (313.0 ppm), which in turn indicates the presence of C=N in the structure
of the compound rather than NH as would be in the case of compound 2′g. The assignment of H4 (s,
7.61 ppm) and C4 (116.9 ppm) is confirmed by the cross peaks in the HMBC (1H-13C) with C4 on
H5, and with H5 and H4 on C8a (140.5 ppm). Similarly, the localized position of C2 on cross peaks
in the HMBC (1H-13C) with H2,6 in the aryl component (d, 7.99 ppm, J = 8.1 Hz) and H4 on the
quinolone carbon with the CS 150.2 ppm. The complete assignment of the spectra is given in the
1
Experimental section. Figure 1 shows the aromatic region of the H and 13C NMR spectra of
quinolone 2g (a) and principal NMR correlation (b). Other two-dimensional spectra are given in the
SI.

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(a)
(b)
Fig. 1. Part of the (1H,13C) spectrum of quinoline 2g in DMSO-d6 (303K) with the assignment of the
most important cross-peaks (a); structure of 2g with the numbering of atoms with principal NMR
correlation (1H-13C HMBC, black arrows; 1H-15N HMBC, purple arrow) used for the identification of
the structure (b).
The formation of 2-aryl-3-hydroxyquinolines 2 probably involves the prior reduction of (2-(2-
nitrophenyl)oxiran-1-yl)(aryl)methanones (1) to give the corresponding (2-(2-aminophenyl)oxiran-
1-yl)(aryl)methanones (A). Then this reduction product is subjected to the Meinwald rearrangement19
with the formation α-diketone B, which through the enol form C undergoes a facile ring closure to
give quinoline. In this case it should be pointed out that the formation of the final product can also
take place through the reductive cyclization of the intermediate D formed in the first stage of the
reaction as a result of the Meinwald rearrangement of trans-(2-(2-nitrophenyl)oxiran-1-
yl)(aryl)methanones 1a-h.
The synthesis of trans-(2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones (1a-h) for reductive
cyclization was performed according to the general procedure for the Darzens condensation19c,20 with
the use of corresponding 2-nitrobenzaldehydes 3a,b and (halomethyl)arylketones 4a-e and MeONa
in MeOH at room temperature for 15 min (Table 2).
Table 2. Synthesis of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones.
Entry
R
H
Cl
H
Cl
H
H
4a,b
4a
4a
4b
4b
4c
Hal
Cl
Cl
Cl
Cl
Br
Cl
Ar
Ph
Ph
Product Yield,c %
3
1
2
3
4
5
6
95
98
99
98
97
98
3a
3b
3a
3b
3a
3a
1a
1b
1c
1d
1e
1f
4-ClC6H4
4-ClC6H4
2-BrC6H4
4-MeC6H4
4d

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7
8
Cl
H
Cl
Cl
4-MeC6H4
99
99
3b
3a
4d
4e
1g
1h
4-MeOC6H4
a
o
(
Chloromethyl)arylketones 4a,b,d,e were obtained on a 0.1 mol scale at 5-10 C by reaction of 1 equiv.
chloroacetylchloride with benzene, chlorobenzene, toluene and anisole, respectively, with the use of 1.5 equiv.
AlBr3.
b(Bromomethyl)(2-bromophenyl)ketone 4c was obtained on a 0.1 mol scale at 50-55 oC by the reaction of
1 equiv. 1-(2-bromophenyl)ethanone with the use of 1 equiv. bromine in ethanol.
cYields refer to isolated products.
We also obtained 3-hydroxy-2-methylquinoline 2i by the Na2S2O4-mediated reductive cyclization
of (2-(2-nitrophenyl)oxiran-1-yl)ethan-2-one 1i with excellent yield, which in turn had been
synthesized from 2-nitrobenzaldehyde and chloroacetone under the Darzens condensation conditions
(Scheme 2). Quinoline 2i as an analogue of α-picoline21 opens up an additional applications of this
methodology in organic synthesis.
Scheme 2. Synthesis of 3-hydroxy-2-methylquinoline.
When this article was ready for publication, we have found that as early as 1954 the synthesis of 3-
hydroxy-2-phenylquinoline (2a) with 70% yield had been carried out by the reduction of (2-(2-
nitrophenyl)oxiran-1-yl)(phenyl)methanone (1a) with Raney nickel in ethyl acetate under 3 atm. of
hydrogen for 2 hours.22 However, until recently this method of synthesis has not been noticed and
appreciated by the scientific community, presumably because the method of reduction and the rather
time-consuming procedures used in the synthesis of the original o-nitrobenzalacetophenone oxide
were not very convenient. We have significantly simplified the process of reduction and the method
of the synthesis of benzalacetophenone oxides proved perfectly simple, short and effective. The
method proposed by us makes it more simple to synthesize 3-hydroxyquinolines with a variety of
substituents in position 2 and with the free position 4 in which can be introduced any substituent, in
particular halogen.23 This method appears preferable to that widely used for the 3-hydroxy-2-
arylquinolines, based on decarboxylation at reflux in a high-boiling solvent (nitrobenzene, diphenyl
ether) of 3-hydroxyquinoline-4-carboxylic acids obtained, in turn, by the Pfitzinger reaction of
isatins with α-hydroxy or α-acetoxy ketones.14a,c,d Isatins that are not commercially available can be
prepared from anilines via the Sandmeyer isatin synthesis24 or o-lithiation and cyclization.25
Assuming that the derivatives of 3-hydroxyquinoline in some reactions behave similarly to the
derivatives of 2-hydroxynaphthalene (naphthalen-2-ol),23a we carried out the bromination of the 3-
hydroxyquinolines using molecular bromine in boiling methanol.23a-c The reaction proceeds in
boiling methanol with the formation of the corresponding 4-bromo-3-hydroxy-2-arylquinolines in
high yields (Table 3).
Table 3. Synthesis of 4-bromo-3-hydroxy-2-arylquinolines.
Entry
1
R
Ph
Product
Yield,a %
93
2
2a
5a

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2
3
4
5
4-ClC6H4
4-MeC6H4
4-MeOC6H4
Me
98
95
93
99
2c
2f
5c
5f
2h
2i
5h
5i
aYields refer to isolated products.
The structures of compounds 5 were established by a variety of NMR methods (see SI) and the
structure of 5h was further confirmed by single-crystal X-ray analysis (Figure 2).26,27
Fig. 2. ORTEP plot of 4-bromo-2-(4-methoxyphenyl)quinolin-3-ol (5h) and partial numbering
scheme. Displacement ellipsoids are drawn at the 30% probability level. H-atoms are represented in
the stick mode for clarity.
Bromo derivatives of 3-hydroxy quinolines have been prepared previously according to three
reported methods; a) through a one-step decarboxylation and bromination of quinoline salicylic acids
o
using bromine and DMF at 80 C ,23c b) through the direct bromination of 3-hydroxy quinoline
o
derivatives, using bromine and DMF at room temperature23c or bromine and AcOH at 70-80 C23a
and c) through bromodecarboxylation at room temperature of quinoline salicylic acids upon
treatment with N-bromosuccinimide in THF.23d These methods are based on quinoline salicylic acids
and as a consequence are labor-consuming and multistage. In this work some simple approaches to
the synthesis of 3-hydroxyquinolines and their 4-bromo derivatives are described.
3. Conclusion
In summary, we have developed an efficient in situ Meinwald rearrangement/intramolecular
reductive cyclization of o-nitrobenzalacetophenone oxides to construct 3-hydroxyquinolines in high
yields under mild reaction conditions. A plausible mechanism was proposed. The practical method is
of satisfactory functional group compatibility. Moreover, further elaboration successfully furnished
4-bromo substituted derivatives which may provide a promising potential application in exploring
biologically active 3-hydroxyquinolines.
4. Experimental section
4.1. General methods

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Melting points were determined on a hot-stage apparatus. Infrared (IR) spectra were recorded on an
FT-IR spectrometer. Elemental analyses for C, H, N were performed on a EVROVECTOR 3000
analyser, and the total content of halogens was determined by the gravimetric method of burning it in
an oxygen flow in the laboratory of Elemental analysis at the A.E. Arbuzov Institute of Organic and
Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences. The high
resolution MALDI mass-spectra were obtained on an UltraFlex III TOF/TOF instrument in positive
reflectron mode; 2.5-DHB and p-NA were used as matrix and PEG-400 was used for calibration of
accurate masses. Nuclear magnetic resonance (NMR) spectra were recorded on Brucker
1
spectrometers Avance III-500 (500.1 MHz for H, 125.8 MHz for 13C and 50.7 MHz for 15N) in
DMSO-d6 at 303 K. The spectrometers were equipped with a pulsed gradient unit capable of
producing magnetic field pulse gradients in the z-direction of 53.5 G cm1. All the spectra were
obtained in a 5-mm gradient broad band probehead. Chemical shifts are reported on the δ (ppm)
1
scale and are relative to the residual H and 13C signal of DMSO-d6. 15N chemical shifts were
referred to the 15N signal of MeCN (235.50 ppm).
4.2. Typical procedure for Darzens reaction
A solution of MeONa obtained by reacting Na (0.73 g, 0.032 mol) in MeOH (20 mL) was added
to a stirred solution of 2-nitrobenzaldehyde (0.027 mol) and a corresponding chloromethylketone
(0.027 mol) in MeOH (70 mL) at room temperature. After 15 min the resulting white precipitate was
filtered off, washed with water (2×25 mL) and dried in air to yield the pure samples of trans-isomer
1 (in the case when chloracetone was used, a precipitate was not formed, and the stirring was
continued for further 7 h, and then the mixture was allowed to react overnight). The mixture was
quenched carefully with water (3×50 mL) and with saturated NH4Cl (1×10 mL), and the product was
1
13
isolated as a thick dark oil. H and C NMR spectra and melting points of 1g-i were in accordance
with our previous syntheses,19с the characteristic data for the compounds 1a-f,j are given below.
4.2.1. trans-(2-(2-Nitrophenyl)oxiran-1-yl)(phenyl)methanone (1a)
Yield: 6.91 g (95%), white powder, mp 114-115 °C (110 °C,28 113-115 °C,22118 °C,29 69-70 °C,30
109-110 °C,31 105-107 °C32); IR (Nujol): υ 1686, 1520 cm-1; 1H NMR (500 MHz, DMSO-d6): δ 4.57
(1 H, d, J 2.0 Hz, H1a), 4.74 (1 H, d, J 2.0 Hz, H1b), 7.56 (2 H, dd, J 7.7, 7.7 Hz, H3-Аr2, H5-Ar2),
7.64 (1 H, dd, J 8.1, 0.9 Hz, H6-Ar1), 7.70 (1 H, ddd, J 8.1, 8.1, 0.9 Hz, H4-Ar1), 7.70 (1 H, dd, J
7.7, 7.7, H4-Ar2), 7.86 (1 H, ddd, J 8.1, 8.1, 1.0 Hz, H4-Ar2), 8.08 (2 H, dd, J 7.7, 1.3 Hz, H2- Ar2,
H6-Ar2), 8.20 (1 H, dd, J 8.1, 1.0 Hz, H3-Ar1); 13C{1H} NMR (126 MHz, DMSO-d6,): δ 193.0
(C1c), 147.6 (C2-Ar1), 135.2 (C1-Ar2), 134.8 (C5-Ar1), 134.3 (C4-Ar2), 132.4 (C1-Ar1), 129.7
(C4-Ar1), 129.0 (C3,C5-Ar2), 128.5 (C2,C6-Ar2), 127.1 (C6-Ar1), 124.8 (C3-Ar1), 58.4 (C1b), 56.8
(C1a); HRMS (MALDI), m/z: calcd. for C15H11NO4 [M+Cs]+ 401.9737, found 401.9766; anal. сalcd
for С15Н11NO4: C, 66.91; H, 4.12; N, 5.20. Found: C, 67.01; H, 4.15; N, 5.18.
4.2.2. trans-(2-(5-Chloro-2-nitrophenyl)oxiran-1-yl)(phenyl)methanone (1b)
1
Yield: 8.04 g (98%), white powder, mp 154-155 °C; IR (Nujol): υ 1690, 1530 cm-1; H NMR (500
MHz, DMSO-d6): δ 4.62 (1 H, d, J 2.0 Hz, Н1a), 4.84 (1 H, d, J 2.0 Hz, H1b), 7.57 (2 H, dd, J 7.6,
7.6 Hz, H3-Ar2, H5-Ar2), 7.59 (1 H, d, J 2.2 Hz, H6-Ar1), 7.72 (1 H, dd, J =7.6, 7.6 Hz, H4-Ar2),
7.75 (1 H, dd, J = 8.8, 2.2 Hz, H4-Ar1), 8.09 (2 H, d, J = 7.6 Hz, H2-Ar2, H6-Ar2), 8.24 (1 H, d, J =

8
ACCEPTED MANUSCRIPT
13
8.8 Hz, H3-Ar1); C{1H} NMR (126 MHz, DMSO-d6): δ 192.5 (C1c), 146.2 (C2-Ar1), 139.5 (C5-
Ar1), 135.0 (C1-Ar2), 134.8 (C1-Ar1), 134.2 (C4-Ar2), 129.4 (C4-Ar1), 128.9 (C3, C5-Ar2), 128.4
(C2,C6-Ar2), 126.8 (C3-Ar1), 126.7 (C6-Ar1), 58.4 (C1b), 56.8 (C1a); HRMS (MALDI), m/z: calcd.
for C15H1035ClNO4 [M+Cs]+ 435.9347, found 435.9372; anal. calcd for C15H1035ClNO4: C, 59.32; H,
3.32; Cl, 11.67; N, 4.61. Found: C, 58.99; H, 3.28; Cl, 11.69; N, 4.58.
4.2.3. trans-(4-Chlorophenyl)(2-(2-nitrophenyl)oxiran-1-yl)methanone (1c)
1
Yield: 8.12 g (99%), white powder, mp 158-160 °C; IR (Nujol): υ 1694, 1679, 1528, 1530 cm-1; H
NMR (500 MHz, DMSO-d6): δ 4.58 (1 H, d, J 2.0 Hz, H1a), 4.76 (1 H, d, J 2.0 Hz, H1a), 7.64 (2 H,
d, J 8.5 Hz, H3-Ar2, H5-Ar2), 7.65 (1 H, d, J 8.2 Hz, H6-Ar1), 7.68 (1 H, dd, J 8.2, 8.2 Hz, H4-Ar1),
7.87 (1 H, dd, J 8.2, 8.2 Hz, H5-Ar1), 8.10 (2 H, d, J 8.5 Hz, H2 and H6-Ar2), 8.21 (1 H, d, J 8.2
Hz, H3-Ar1); 13C{1H} NMR (126 MHz, DMSO-d6): δ 191.9 (C1c), 147.5 (C2-Ar1), 139.1 (C4-Ar2),
134.7 (C5-Ar1), 133.7 (C1-Ar2), 132.3 (C1-Ar1), 130.3 (C2, C6-Ar2), 129.6 (C4-Ar1), 129.0 (C3,
C5-Ar2), 127.0 (C6-Ar1), 124.7 (C3-Ar1), 58.5 (C1b), 57.4 (C1a); HRMS (MALDI), m/z: calcd. for
C15H1035ClNO4 [M+Cs]+ 435.9347, found 435.9355; anal. calcd for C15H10ClNO4: C, 59.32; H, 3.32;
Cl, 11.67; N, 4.61. Found: C, 59.85; H, 3.22; Cl, 11.59; N, 4.60.
4.2.4. trans-(2-(5-Chloro-2-nitrophenyl)oxiran-1-yl)(4-chlorophenyl)methanone (1d)
1
Yield: 8.95 g (98%), white powder, mp 168-169 °C; IR (Nujol): υ 1687, 1515 cm-1; H NMR (500
MHz, DMSO-d6): δ 4.59 (1 H, d, J 2.0 Hz, H1a), 4.81 (1 H, d, J 2.0 Hz, H1b), 7.58 (1 H, d, J 2.3 Hz,
H6-Ar1), 7.62 (2 H, d, J 8.5 Hz, H3-Ar2, H5-Ar2), 7.74 (1 H, dd, J 8.5, 2.3 Hz, H4-Ar1), 8.08 (2 H,
13
d, J 8.5 Hz, H2-Ar2, H6-Ar2), 8.23 (1 H, d, J 8.5 Hz, H3-Ar1); C{1H} NMR (126 MHz, DMSO-
d6): δ 191.8 (C1c), 146.2 (C2-Ar1), 139.7 (C5-Ar1), 139.4 (C4-Ar2), 134.8 (C1-Ar1), 133.7 (C1-
Ar2), 130.5 (C2, C6-Ar2), 129.6 (C4-Ar1), 129.1 (C3, C5-Ar2), 127.0 (C3-Ar1), 126.8 (C6-Ar1),
58.5 (C1b), 57.0 (C1a); HRMS (MALDI), m/z: calcd. for C15H9 Cl2NO4 [M+Cs]+ 469.8958;
35
35
C15H9 Cl37ClNO4 [M+Cs]+ 471.8931, found 469.8985; 471.8960; anal. calcd for C15H9Cl2NO4: C,
53.28; H, 2.68; Cl, 20.97; N, 4.14. Found: C, 53.42; H, 2.62; Cl, 20.85; N, 4.18.
4.2.5. trans-(2-Bromophenyl)(2-(2-nitrophenyl)oxiran-1-yl)methanone (1e)
1
Yield: 9.12 g (97%), white powder, mp 86-87 °C; IR (Nujol): υ 1699, 1684, 1535, 1524 cm-1; H
NMR (500 MHz, DMSO-d6): δ 4.348 (1 H, d, J 2.0 Hz, H1b), 4.645 (1 H, d, J 2.0 Hz, H1a), 7.48-
7.62 (2 H, m, H4-Ar2, H5-Ar2), 7.58 (1 H, dd, J 8.4, 0.9 Hz, H6-Ar1), 7.66 (1 H, ddd, J 8.4, 8.4, 0.9
Hz, H4-Ar1), 7.73 (1 H, dd, J 7.4, 1.8 Hz, H6-Ar2), 7.77 (1 H, dd, J 7.4, 1.8 Hz, H3-Ar2), 7.83 (ddd,
J = 8.4, 8.4, 0.9 Hz, 1H, H5-Ar1), 8.19 (1 H, dd, J = 8.4, 0.9 Hz, H3-Ar1); 13C{1H} NMR (126 MHz,
DMSO-d6): δ 199.5 (C1c), 147.5 (C2-Ar1), 137.4 (C1-Ar2), 134.7 (C5-Ar1), 133.6 (C3-Ar2), 133.2
(C4-Ar2), 131.8 (C1-Ar1), 129.8 (C6-Ar2), 129.7 (C4-Ar1), 127.8 (C5-Ar2), 126.8 (C6-Ar1), 124.7
(C3-Ar1), 119.0 (C2-Ar2), 60.3 (C1b) 57.4 (C1a); HRMS (MALDI), m/z: calcd. for C15H1079BrNO4
[M+Cs]+ 479.8842; C15H1081BrNO4 [M+Cs]+ 481.8823, found 479.8855; 481.8852; anal. calcd for
C15H10BrNO4: C, 51.75; H, 2.90; Br, 22.95; N, 4.02. Found: C, 51.85; H, 2.92; Br, 22.83; N, 4.07.

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4.2.7. trans-1-(3-(2-Nitrophenyl)oxiran-2-yl)ethanone (1i)
1
Yield: 5.54 g (99%), dark brown oil; IR (Nujol): υ 1715, 1526 cm-1; H NMR (500 MHz, DMSO-
d6): δ 2.21 (3 H, s, Me), 3.67 (1 H, d, J 2.1 Hz, H8), 4.65 (1 H, d, J 2.1 Hz, H7), 7.54 (1 H, dd, J 7.9,
1.1 Hz, H6), 7.66 (1 H, ddd, J = 7.9, 7.9, 1.1 Hz, H4), 7.82 (1 H, ddd, J = 7.9, 7.9, 1.1 Hz, H3), 8.18
(1 H, dd, J 7.9, 1.1 Hz, H5); 13C{1H} NMR (126 MHz, DMSO-d6): δ 203.2 (C9), 147.4 (C2), 134.7
15
(C3), 132.1 (C1), 129.6 (C4), 126.8 (C6), 124.7 (C5), 61.2 (C8), 55.7 (C7), 25.5 (C10); N NMR
(51 MHz; DMSO-d6): δ 371.8 (N1-Q); HRMS (MALDI), m/z: calcd. for C10H9NO4 [M+Cs]+
339.9581, found 339.9601; anal. calcd for C10H9NO4: C, 57.97; H, 4.38; N, 6.76. Found: C, 57.63;
H, 4.41; N, 6.70.
4.3. Typical procedure for the synthesis of 2-arylquinolin-3-ols
A solution of Na2S2O4 (2.61 g, 15 mmol) in H2O (200 mL) was added to a solution of (2-(2-
nitrophenyl)oxiran-1-yl)(aryl)methanone (3 mmol) in dioxane (200 mL). The reaction mixture after
stirring at reflux for 3 h was allowing to cool to room temperature and was poured into water (500
mL). The resulting precipitate was filtered off, washed with water (2×50 mL) and dried in air to give
an analytically pure product 2.
4.3.1. 2-Phenylquinolin-3-ol (2a)
Yield 0.61 g (92%), yellow powder, mp 223-224 °C (220-221 °C,22 225-227 °C14d); IR (Nujol): υ
1
3314, 1596, 1193, 697 cm-1; H NMR (500 MHz, DMSO-d6): δ 7.43-7.60 (5 H, m, H3-Ar, H4-Ar,
H5-Ar, H6-Q, H7-Q), 7.65 (1 H, s, H4-Q), 7.80 (1 H, d, J 8.0 Hz, H5-Q), 7.94 (1 H, d, J 8.0 Hz, H8-
Q), 8.07 (2 H, d, J 8.1 Hz, H2-Ar, H6-Ar), 10.51 (1 H, s, OH); 13C{1H} NMR (DMSO-d6, 126
MHz): δ 149.9 (C2-Q), 149.4 (C3-Q), 142.2 (C8a-Q), 137.8 (C1-Ar), 129.4 (C2 and C6-Ar), 128.7
(C4-Ar), 128.6 (C8-Q), 128.5 (C4a-Q), 127.7 (C3 and C5-Ar), 126.5 (C6-Q), 126.1 (C7-Q), 125.8
(C5-Q), 116.8 (C4-Q); 15N NMR (51 MHz, DMSO-d6,): δ 313.2 (N1-Q); HRMS (MALDI), m/z:
calcd. for C15H11NO [M+Cs]+ 353.9890, found 353.9875; anal. calcd for C15H11NO: C, 81.43; H,
5.01; N, 6.33. Found: C, 81.58; H, 5.20; N, 6.01.
4.3.2. 6-Chloro-2-phenylquinolin-3-ol (2b)
1
Yield 0.71 g (93%), yellow powder, mp 219-220 °C; IR (Nujol): υ 3437, 1598, 1192, 695 cm-1; H
NMR (500 MHz, DMSO-d6): δ 7.44-7.53 (4 H, m, H3-Ar, H4-Ar, H5-Ar, H7-Q), 7.64 (1 H, s, H4-
Q), 7.93 (1 H, d, J 8.9 Hz, H8-Q), 7.95 (1 H, d, J 2.3 Hz, H5-Q), 8.56 (2 H, dd, J 8.3, 1.7 Hz, H2-Ar,
H6-Ar), 10.81 (1 H, br s, OH); 13C{1H} NMR (DMSO-d6, 126 MHz): δ 150.5 (C2-Q), 150.3 (C3-Q),
140.5 (C8a-Q), 137.5 (C1-Ar), 130.9 (C6-Q), 130.6 (C8-Q), 129.6 (C4a-Q), 129.4 (C2 and C6-Ar),
128.7 (C4-Ar), 127.7 (C3 and C5-Ar), 126.5 (C7-Q), 124.5 (C5-Q), 116.0 (C4-Q); 15N NMR (51
MHz, DMSO-d6): δ 314.0 (N1-Q); HRMS (MALDI), m/z: calcd. for C15H1035ClNO [M+Cs]+

10
ACCEPTED MANUSCRIPT
387.9500, found 387.9519; anal. calcd for C15H10ClNO: C, 70.46; H, 3.94; Cl, 13.87; N, 5.48.
Found:С, 71.02; Н, 3.85; N, 5.51.
4.3.3. 2-(4-Chlorophenyl)quinolin-3-ol (2c)
1
Yield 0.75 g (98%), yellow powder, mp 244-245 °C; IR (Nujol): υ 3396, 1602, 1193, 748 cm-1; H
NMR (500 MHz, DMSO-d6): δ 7.46-7.54 (2 H, m, H6-Q, H7-Q), 7.54 (2 H, d, J 8.1 Hz, H3-Ar, H5-
Ar), 7.67 (1 H, s, H4-Q), 7.80 (1 H, d, J 7.8 Hz, H5-Q), 7.94 (1 H, d, J 8.1 Hz, H8-Q), 8.14 (2 H, d, J
13
= 8.1Hz, H2-Ar, H6-Ar2), 10.69 (1 H, s, OH); C{1H} NMR (126 MHz, DMSO-d6): δ 149.5 (C3-
Q), 148.4 (C2-Q), 142.2 (C8a-Q), 136.6 (C1-Ar), 133.4 (C4-Ar), 131.2 (C2,C6-Ar), 128.8 (C4a-Q),
128.7 (C8-Q), 127.8 (C3 and C5-Ar), 126.7 (C6-Q), 126.3 (C7-Q), 125.9 (C5-Q), 117.1 (C4-Q); 15N
NMR (51 MHz, DMSO-d6): δ 313.6 (N1-Q); HRMS (MALDI), m/z: calcd. for C15H1035ClNO
[M+Cs]+ 387,9500, found 387,9526; anal. calcd for C15H10ClNO: C, 70.46; H, 3.94; Cl, 13.87; N,
5.48. Found: C, 70.02; H, 4.00; Cl, 13.83; N, 5.41.
4.3.4. 6-Chloro-2-(4-chlorophenyl)quinolin-3-ol (2d)
Yield 0.77 g (89%), green powder, mp 230-232 °C; IR (Nujol): υ 3315, 1597, 1176, 1079, 1011, 813
cm-1; 1H NMR (500 MHz, DMSO-d6): δ 7.50 (1 H, dd, J 8.9, 2.0 Hz, H7-Q), 7.54 (2 H, d, J 8.5 Hz,
H3-Ar, H5-Ar), 7.64 (1 H, s, H4-Q), 7.93 (1 H, d, J 8.9 Hz, H8-Q), 7.96 (1 H, d, J 2.0 Hz, H5-Q),
8.12 (2 H, d, J 8.5 Hz, H2-Ar, H6-Ar), 10.90 (1 H, s, OH). 13C{1H} NMR (126 MHz, DMSO-d6): δ
150.2 (C2-Q), 148.9 (C3-Q), 140.5 (C8a-Q), 136.2 (C1-Ar), 133.6 (C4-Ar), 131.2 (C2 and C6-Ar),
131.1 (C4a-Q), 130.6 (C8-Q), 129.7 (C6-Q), 127.8 (C3,C5-Ar), 126.7 (C7-Q), 124.5 (C5-Q), 116.3
(C4-Q); 15N NMR (51 MHz, DMSO-d6): δ 313.6 (N1-Q); HRMS (MALDI), m/z: calcd. for
35
35
C15H9 Cl2NO [M+Cs]+ 421.9110; C15H9 Cl37ClNO [M+Cs]+ 423.9083, found 421.9089; 423.9102;
anal. calcd for C15H9Cl2NO: C, 62.09; H, 3.13; Cl, 24.44; N, 4.83. Found: C, 61.93; H, 3.02; Cl,
24.15; N, 4.78.
4.3.5. 2-(2-Bromophenyl)quinolin-3-ol (2e)
Yield 0.77 g (85%), brown powder, mp 232-235 °C (244-245 oC14c); IR (Nujol): υ 3400, 1602, 1193,
746 cm-1; 1H NMR (500 MHz, DMSO-d6): δ 7.40 (1 H, ddd, J = 8.0, 8.0, 2.1 Hz, H4-Ar), 7.47 (1 H,
ddd, J = 8.0, 8.0, 2.1 Hz, H5-Ar), 7.49 (1 H, d, J 8.0 Hz, H3-Ar), 7.52-7.56 (2 H, m, H6-Q, H7-Q),
7.68 (1 H, s, H4-Q), 7.73 (1 H, d, J 8.0 Hz, H6-Ar), 7.87 (1 H, d, J 7.6 Hz, H5-Q), 7.92 (1 H, d, J 7.9
13
Hz, H8-Q), 10.50 (1 H, s, OH); C{1H} NMR (126 MHz; DMSO-d6): δ 151.8 (C2-Q), 149.1 (C3-
Q), 141.2 (C8a-Q), 139.1 (C1-Ar), 132.0 (C6-Ar), 131.1 (C5-Ar), 130.0 (C4-Ar), 129.2 (C4a-Q),
128.1 (C8-Q), 127.3 (C3-Ar), 127.0 (C6-Q), 126.4 (C7-Q), 126.2 (C5-Q), 122.3 (C2-Ar), 116.6 (C4-
Q); HRMS (MALDI), m/z: calcd. for C15H1079BrNO [M+Cs]+ 431.8995; C15H1081BrNO [M+Cs]+
433.8976, found 431.9000; 433.8991; anal. calcd for C15H10BrNO: C, 60.02; H, 3.36; Br, 26.62; N,
4.67. Found: C, 59.92; H, 3.32; Br, 26,71; N, 4.53.
4.3.7. 2-(4-Tolyl)quinolin-3-ol (2f)

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Yield 0.64 g (91%), yellow powder, mp 251-252 °C; IR (Nujol): υ 3438, 1603, 1196 cm-1; 1H NMR
(500 MHz, DMSO-d6): δ 2.38 (3 H, s, Me), 7.29 (2 H, d, J 8.0 Hz, H3-Ar, H5-Ar), 7.47 (1 H, dd, J
8.0, 8.0 Hz, H6-Q), 7.52 (1 H, dd, J 8.0, 8.0 Hz, H7-Q), 7.63 (1 H, s, H4-Q), 7.79 (1 H, d, J 8.0 Hz,
H5-Q), 7.92 (1 H, d, J 8.0 Hz, H8-Q), 8.00 (2 H, d, J 8.0 Hz, H2-Ar, H6-Ar), 10.48 (1H, s, OH);
13C{1H} NMR (126 MHz; DMSO-d6): δ 149.8 (C2-Q), 149.5 (C3-Q), 142.0 (C8a-Q), 138.0 (C4-Ar),
134.9 (C1-Ar), 129.4 (C2 and C6-Ar), 128.5 (C4a-Q), 128.4 (C8-Q), 128.3 (C3 and C5-Ar), 126.4
(C6-Q), 126.1 (C7-Q), 125.8 (C5-Q), 116.8 (C4-Q), 20.9 (C4a-Ar); 15N NMR (51 MHz, DMSO-d6):
δ 311.5 (N1-Q); HRMS (MALDI), m/z: calcd. for C16H13NO [M+Cs]+ 368.0046, found 368.0058;
anal. calcd for C16H13NO: C, 81.68; H, 5.57; N, 5.95. Found: C, 81.31; H, 5.53; N, 5.98.
4.3.8. 6-Chloro-2-(4-tolyl)quinolin-3-ol (2g)
1
Yield 0.74 g (91%), white powder, mp 254-256 °C; IR (Nujol): υ 3454, 1597, 1189, 813 cm-1; H
NMR (500 MHz, DMSO-d6): δ 2.38 (3 H, s, Me), 7.29 (2 H, d, J 8.1 Hz, H3-Ar, H5-Ar), 7.49 (1 H,
dd, J 8.9, 2.3 Hz, H7-Q), 7.61 (1 H, s, H4-Q), 7.92 (1 H, d, J 8.9 Hz, H8-Q), 7.94 (1 H, d, J 2.3 Hz,
H5-Q), 7.99 (2 H, d, J 8.1 Hz, H2-Ar, H6-Ar), 10.72 (1 H, s, OH). 13C{1H} NMR (126 MHz,
DMSO-d6); δ 150.2 (C2-Q), 150.3 (C3-Q), 140.5 (C8a-Q), 138.2 (C4-Ar), 134.6 (C1-Ar), 130.7 (C6-
Q), 130.6 (C8-Q), 129.5 (C4a-Q), 129.5 (C2 and C6-Ar), 128.4 (C3 and C5-Ar), 126.5 (C7-Q), 124.4
(C5-Q), 116.9 (C4-Q), 20.9 (C4a-Q); HRMS (MALDI), m/z: calcd. for C16H1235ClNO [M+Cs]+
401.9656, found 401.9643; anal. calcd for C16H12ClNO: C, 71.25; H, 4.48; Cl, 13.14; N, 5.19.
Found: C, 71.38; H, 4.51; Cl, 13.19; N, 5.15.
4.3.9. 2-(4-Methoxyphenyl)quinolin-3-ol (2h)
Yield 0.74 g (98%), yellow powder, mp 246-247 °C; IR (Nujol): υ 3435, 1593, 1248, 1177 cm-1; 1H
NMR (500 MHz, DMSO-d6): δ 3.83 (3 H, s, OMe), 7.04 (2H, d, J 8.9 Hz, H3-Ar, H5-Ar), 7.45 (1 H,
ddd, J 8.1, 8.1, 1.4 Hz, H6-Q), 7.50 (1 H, ddd, J 8.1, 1.4 Hz, H7-Q), 7.60 (1 H, s, H4-Q), 7.77 (1 H,
dd, J 8.1, 1.4 Hz, H5-Q), 7.91 (1 H, d, J 8.1 Hz, H8-Q), 8.12 (2 H, d, J 8.9 Hz, H2-Ar, H6-Ar),
13
10.48 (1 H, s, OH); C{1H} NMR (126 MHz, DMSO-d6): δ 159.7 (C4-Ar), 149.4 (C2-Q), 149.4
(C3-Q), 142.2 (C8a-Q), 130.9 (C2 and C6-Ar), 130.2 (C1-Ar), 128.5 (C8-Q), 128.4 (C4a-Q), 126.2
(C6-Q), 126.1 (C7-Q), 125.7 (C5-Q), 116.6 (C4-Q), 113.2 (C3 and C5-Ar), 55.1 (C4a-Ar); HRMS
(MALDI), m/z: calcd. for C16H13NO2 [M+Cs]+ 383.9995, found 384.0017; anal. calcd for
C16H13NO2: C, 76.48; H, 5.21; N, 5.57. Found: C, 76.41; H, 5.24; N, 5.61.
4.3.10. 2-Methylquinolin-3-ol (2i)
1
Yield 0.47 g (98%), brown powder, mp 269-271 °C; IR (Nujol): υ 1605, 1237, 1176, 746 cm-1; H
NMR (500 MHz, DMSO-d6): δ 2.54 (3 H, s, Me), 7.40 (1 H, ddd, J 8.1, 8.1, 1.4 Hz, H6-Q), 7.43 (1
H, s, H4-Q), 7.45 (1 H, ddd, J 8.1, 8.1, 1.4 Hz, H7-Q), 7.72 (1 H, dd, J 8.1, 1.4 Hz, H5-Q), 7.82 (1 H,
dd, J 8.1, 1.4 Hz, H8-Q), 10.31 (1 H, s, OH); 13C{1H} NMR (126 MHz, DMSO-d6): δ 151.9 (C3-Q),
149.6 (C2-Q), 141.6 (C8a-Q), 128.5 (C4a-Q), 127.6 (C8-Q), 125.9 (C5-Q), 125.7 (C6-Q), 125.6 (C7-

12
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15
Q), 114.3 (C4-Q), 20.1 (Me); N NMR (51 MHz, DMSO-d6): δ 310.2 (N1-Q); HRMS (MALDI),
m/z: calcd. for C10H9NO [M+Cs]+ 291.9733, found 291.9729; anal. calcd for C10H9NO: C, 75.45; H,
5.70; N, 8.80. Found:C, 75.69; H, 5.68; N, 8.72.
4.4. Typical procedure for the synthesis of 4-bromo-2-arylquinolin-3-ols
Br2 (0.15 mL, 3 mmol) was added to a stirred solution of 2-arylquinolin-3-ol (2 mmol) 2 in
MeOH (100 mL) at room temperature, and the resulting reaction mixture was heated under reflux for
3 h. An abundant precipitation of crystals occurred during the reaction time in cases when
compounds 2c and 2i were used. The precipitate was filtered off, washed with a solution of MeONa
(2×50 mL) obtained with use of Na (0.18 g, 7.8 mmol) and MeOH (100 mL) and water (3×50 mL),
dried in air to give analytically pure product 5c,i. In the cases when compounds 2a,f,h were used, the
precipitation of crystals in the reaction mixtures did not occur. A solution of MeONa (50 mL)
obtained with Na (0.05 g, 2.2 mmol) and MeOH (50 mL) was added to the reaction mixture, and the
resulting reaction mixture was heated under reflux for a further 1 h. The reaction mixture was
allowed to cool and it was poured into water (200 mL). The resulting precipitate was filtered off,
washed with water (3×50 mL), and dried in air to give an analytically pure product 5a,f,h.
4.3.1. 4-Bromo-2-phenylquinolin-3-ol (5a)
1
Yield 0.56 g (93%), yellow powder, mp 141-142 °C; IR (Nujol): υ 1586, 1131, 767, 701 cm-1; H
NMR (500 MHz, DMSO-d6): δ 7.47-7.53 (2 H, m, H3-Ar, H5-Ar), 7.59-7.68 (1 H, m, H4-Ar), 7.80-
8.02 (4 H, m, H5-Q, H6-Q, H7-Q, H8-Q), 8.25 (2 H, dd, J 8.3, 1.7 Hz, H2-Ar, H6-Ar), 10.12 (1 H, s,
OH); 13C{1H} NMR (DMSO-d6, 126 MHz): δ 151.8 (C2-Q), 146.5 (C3-Q), 142.7 (C8a-Q), 137.5
(C1-Ar), 129.5 (C2-Ar), 129,2 (C8-Q), 128.9 (C4-Ar), 128.1 (C6-Q), 127.9 (C3-Ar), 127.8 (C4a-Q),
127.5 (C7-Q), 125.1 (C5-Q), 117.8 (C4-Q); 15N NMR (DMSO-d6, 51 MHz) δ 3110.6 (N1-Q);
HRMS (MALDI), m/z: calcd. for C15H1079BrNO [M+Cs]+ 431.8995; C15H1081BrNO
[M+Cs]+433.8976, found 431.8988; 433.8982; anal. calcd for C15H10BrNO: C, 60.02; H, 3.36; Br,
26.62; N, 4.67. Found: C, 60.38; H, 3.39; Br, 26.81; N, 4.63.
4.3.2. 4-Bromo-2-(4-chlorophenyl)quinolin-3-ol (5c)
1
Yield 0.66 g (98%), light yellow powder, mp 185-186 °C; IR (Nujol): υ 3375, 752 cm-1; H NMR
(500 MHz, DMSO-d6): δ 7.58 (2 H, d, J 7.6 Hz, H3-Ar, Н5-Аr), 7.64-7.73 (2 H, m, H6-Q, H7-Q),
13
7.96-8.03 (2 H, m, H2-Ar, H6-Ar), 7.99-8.05 (2 H, m, H5-Q, H8-Q), 10.26 (1 H, s, OH); C{1H}
NMR (126 MHz, DMSO-d6,): δ 150.4 (C2-Q), 146.4 (C3-Q), 142.5 (C8a-Q), 136.1 (C1-Ar), 133.8
(C4-Ar), 131.3 (C2-Ar), 129.1 (C5-Q), 128.3 (C6-Q), 128.0 (C3-Ar), 127.7 (C4a-Q), 127.6 (C7-Q),
125.1 (C8-Q), 118.1 (C4-Q); 15N NMR (51 MHz, DMSO-d6): δ 309.7 (N1-Q); HRMS (MALDI),
79
81
m/z: calcd. for C15H9 Br35ClNO [M+H]+ 333.9629; C15H9 Br35ClNO [M+H]+ 335.9607, found
333.9636; 335.9622; anal. calcd for C15H9BrClNO: C, 53.84; H, 2.71; Br, 23.88; Cl, 10.60; N, 4.19.
Found: C, 53.51; H, 2.72; Br + Cl, 33.90; N, 4.68.
4.3.4. 4-Bromo-2-(4-tolyl)quinolin-3-ol (5f)

13
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1
Yield 0.60 g (95%), yellow powder, mp 149-150 °C; IR (Nujol): υ 3433, 759 cm-1; H NMR (500
MHz, DMSO-d6): δ 2.39 (3 H, s, Me), 7.32 (2 H, d, J 8.0 Hz, H3-Ar, H5-Ar), 7.63-7.69 (2 H, m, H6-
Q, H7-Q), 7.88 (2 H, d, J = 8.0 Hz, H2-Ar, H6-Ar), 7.96-8.03 (2 H, m, H5-Q, H8-Q), 10.08 (1H, s,
OH); 13C{1H} NMR (126 MHz, DMSO-d6): δ 151.7 (C2-Q), 146.5 (C3-Q), 142.6 (C8a-Q), 138.6
(C4-Ar), 134.6 (C1-Ar), 129.5 (C2-Ar), 129.1 (C5-Q), 128.5 (C3-Ar), 128.0 (C6-Q), 127.5 (C7-Q),
127.4 (C4a-Q), 125.1 (C8-Q), 117.9 (C4-Q), 20.9 (Me); 15N NMR (51 MHz, DMSO-d6): δ 310.5
(N1-Q); HRMS (MALDI), m/z: calcd. for C16H1279BrNO [M+H]+ 314.0175; C16H1281BrNO [M+H]+
316.0156, found 314.0180; 316.0173; anal. calcd for C16H12BrNO: C, 61.17; H, 3.85; Br, 25.43; N,
4.46. Found: C, 61.33; H, 3.88; Br, 25.28; N, 4.37.
4.3.5. 4-Bromo-2-(4-methoxyphenyl)quinolin-3-ol (5h)
Yield 0.61 g (93%), tan powder, mp 150-151 °C; IR (Nujol): υ 1606, 1572, 1256, 1178, 761 cm-1; 1H
NMR (500 MHz, DMSO-d6): δ 3.81 (3 H, s, OMe), 7.04 (2 H, d, J 8.0 Hz, H3-Ar, H5-Ar), 7.59-7.64
(2 H, m, H6-Q, H7-Q), 7.93-8.00 (2 H, m, H5-Q, H8-Q), 8.09 (2 H, d, J 8.0 Hz, H2-Ar, H6-Ar);
13C{1H} NMR (126 MHz, DMSO-d6): δ 160.0 (C4-Ar), 151.2 (C2-Q), 146.5 (C3-Q), 142.5 (C8a-Q),
131.2 (C2-Ar), 129.7 (C1-Ar), 128.8 (C5-Q), 127.8 (C6-Q), 127.5 (C7-Q), 127.2 (C4a-Q), 125.0
(C8-Q), 117.8 (C4-Q), 113.4 (C3-Ar), 55.2 (OMe); 15N NMR (51 MHz, DMSO-d6): δ 305.3 (N1-Q);
HRMS (MALDI), m/z: calcd. for C16H1279BrNO2 [M+Cs]+ 461.9100; C16H1281BrNO2 [M+Cs]+
463.9081, found 461.9119; 463.9066; anal. calcd for C16H12BrNO2: C, 58.20; H, 3.66; Br, 24.20; N,
4.24. Found: C, 58.32; H, 3.30; Br, 24.29; N, 4.18.
4.3.6. 4-Bromo-2-methylquinolin-3-ol (5i)
Yield 0.47 g (99%), light yellow powder, mp 209-211 °C; IR (Nujol): υ 1592, 1559, 1173,748 cm-1;
1H NMR (500 MHz, DMSO-d6): δ 2.54 (3 H, s, Me), 7.40 (ddd, J = 8.1, 8.1, 1.4 Hz, 1H, H6-Q), 7.43
(1H, s, H4-Q), 7.45 (1H, ddd, J 8.1, 8.1, 1.4 Hz, H7-Q), 7.72 (1 H, dd, J 8.1, 1.4 Hz, H5-Q), 7.82 (1
H, dd, J 8.1, 1.4 Hz, H8-Q), 10.31 (1 H, s, OH); 13C{1H} NMR (126 MHz, DMSO-d6): δ 151.9 (C3-
Q), 149.6 (C2-Q), 141.6 (C8a-Q), 128.5 (C4a-Q), 127.6 (C8-Q), 125.9 (C5-Q), 125.7 (C6-Q), 125.6
(C7-Q), 114.3 (C4-Q), 20.1 (Me); 15N NMR (51 MHz, DMSO-d6): δ 310.2 (N1-Q); HRMS
79
81
(MALDI), m/z: calcd. for C10H8 BrNO [M+Cs]+ 369.8838; C10H8 BrNO [M+Cs]+ 371.8818, found
369.8834; 371.8824; anal. calcd for C10H8BrNO: C, 50.45; H, 3.39; Br, 33.56; N, 5.88. Found: C,
50.31; H, 3.41; Br, 33.62; N, 5.90.
Acknwledgements
This work was partially supported by the Russian scientific foundation (grant No. 14-23-00073-п).
Supplementary data

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ACCEPTED MANUSCRIPT
1D and 2D NMR Spectra and HRMS (MALDI) mass-spectra of the products 1a-i, 2a-i and 5a-i;
crystallographic data for 5h (CIF). This material is available free of charge via the Internet at
http://pubs.acs.org.
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2779, R(int) = 0.0515, full matrix least squares on F2, parameters = 186, restrains = 1. Final indices R1 =
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