Synthesis of quinolines via acid-catalyzed cyclodehydration of 2-(Tosylamino)chalcones

Article abstract of DOI:10.1007/s10593-017-2010-3

(Image presented) The acid-catalyzed cyclodehydration of (E)-3-[(2-tosylamino)phenyl]-1-(het)aiylprop-2-en-1-ones to 2-substituted quinolones was investigated. The reaction proceeds via the key step of (E,Z)-isomerization with subsequent intramolecular cy

Full text of DOI:10.1007/s10593-017-2010-3

DOI 10.1007/s10593-017-2010-3
Chemistry of Heterocyclic Compounds 2016, 52(12), 1087–1091
LETTER TO THE EDITOR
Synthesis of quinolines via acid-catalyzed
cyclodehydration of 2-(tosylamino)chalcones
Anton S. Makarov1, Ludmila N. Sorotskaja2,
Maxim G. Uchuskin1,3*, Igor V. Trushkov3,4
1 Perm State University,
15 Bukireva St., Perm 614990, Russia; e-mail: mu@psu.ru
2 Kuban State Technological University,
2 Moskovskaya St., Krasnodar 350072, Russia; e-mail: sorotskaja@rambler.ru
3 Peoples' Friendship University of Russia,
6 Miklukho-Maklaya St., Moscow 117198, Russia
4 Dmitry Rogachev Federal Research Center of Pediatric Hematology,
Oncology and Immunology,
1 Samory Mashela St., Moscow 117997, Russia; e-mail: itrushkov@mail.ru
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2016, 52(12), 1087–1091
Submitted September 25, 2016
Accepted October 26, 2016
The acid-catalyzed cyclodehydration of (E)-3-[(2-tosylamino)phenyl]-1-(het)arylprop-2-en-1-ones to 2-substituted quinolones was inves-
tigated. The reaction proceeds via the key step of (E,Z)-isomerization with subsequent intramolecular cyclization affording the target
compounds in high yields.
Keywords: 2-(het)arylquinolines, aldol condensation, cyclodehydration, (E,Z)-isomerization, Friedlaender synthesis, intramolecular
cyclization.
Quinoline skeleton is presnt in many natural and
synthetic drugs (quinine, mefloquine, chloroquine,
imiquimod) and other biologically active substances (e.g.,
herbicide quinmerac), organocatalysts and ligands for
catalysis (cinchonine, cinchonidine, quinidine), dyes, and
other valuable compounds (Fig. 1).1 It is therefore not
surprising that the development of new and modification of
existing methods of synthesis of quinolines is an important
and urgent task.2
bonds formation (Scheme 1). Path a involves the formation
of imine I1 via the reaction of a ketone with amino group of
aminocarbonyl compound. The subsequent intramolecular
aldol condensation leads to the formation of hydroxyimine
The classical Friedlaender, Skraup, Doebner–Miller,
Conrad–Limpach, Pomeranz–Fritsch, Combes reactions
and other approaches are used to synthesize quinolines.3
Despite the development of new approaches to the
formation of the quinoline skeleton, Friedlaender reaction
remains one of the most common and widely used methods
for the synthesis of quinolines. This is an acid- or base-
catalyzed condensation of o-acylarylamines with carbonyl
compounds containing an active methylene group.4
However, the mechanism of the Friedlaender reaction is
still a matter of discussion. To date, two alternative paths
for the formation of quinolines have been proposed. These
differ by the sequence of the C(3)–C(4) and C(2)–N(1)
Figure 1. Selected useful quinolines.
0009-3122/16/52(12)-1087©2016 Springer Science+Business Media New York
1087

Chemistry of Heterocyclic Compounds 2016, 52(12), 1087–1091
R1
Scheme 1
Scheme 2
O
CHO
Me
R1
KOH
+
O
+
O
EtOH
40°C
O
NH
NH
Ts
NH
R1
Ts
2a–e
R1
Ts
1
3a–e
4a–e
DCE

TfOH
85 C
N
R1
5a–e
Table 1. Yields of chalcones 3а–e and quinolines 5а–e
R1
Chalcone*
Yield, %
Quinoline**
Yield, %
90
Ph
65
3a
3b
3c
3d
3e
5a
5b
5c
5d
5e
4-MeOC6H4
4-MeC6H4
4-FC6H4
70
70
68
96
56
59
95
87
Thiophen-2-yl
* The reaction was conducted with 2.0 mmol loading of compound 1.
** The reaction was conducted with 0.5 mmol loading of compound 3.
I2, aromatization of which gives the desired quinoline. The
basis of path b is an initial aldol condensation forming an
amino alcohol I3 followed by cyclodehydration producing
quinolines via the same intermediate I2.
that the maximum yield of the desired 2-phenylquinoline
(5a) could be achieved upon heating the solution of
chalcone 3a in 1,2-dichloroethane (DCE) for 12 h at 85°C
in the presence of 3 equiv of trifluoromethanesulfonic acid
(TfOH).
Path b is considered to be less preferred due to the ease
of formation of the α,β-unsaturated carbonyl compound I4
bearing (E)-configuration. Its conversion into a quinoline
via (E,Z)-isomerization and subsequent cyclodehydration
was previously considered unlikely. However, recently accu-
mulated data on the formation of intermediates I3,5 α,β-un-
saturated carbonyl compounds I4 and I5,6 as well as the
possibility of their cyclodehydration to quinolines7 suggest
the possibility of quinoline formation via path c. In order to
better understand the mechanism of Friedlaender synthesis,
we studied the cyclodehydration of 2-(tosylamino)-
chalcones to substituted quinolines.
The starting α,β-unsaturated ketones 3a-e were obtained
in 56–70% yields by base-catalyzed aldol condensation of
2-(tosylamino)benzaldehyde (1)8 and the commercially
available ketones 2a–e (Scheme 2, Table 1). Moderate
yields of products 3a–e can be explained by a side reaction
of the conjugate Michael addition of the starting ketone
2a–e to enone 3a–e to form pentane-1,5-dione 4a–e.9 As a
result, when using an equimolar ratio of reagents
incomplete conversion of aldehyde 1 is observed, while the
use of an excess of ketone 2 makes diketone 4 the major
product. In the case of acetophenone (2a) the by-product 4a
was isolated and characterized.
We examined the scope of the cyclodehydration reaction
using the optimized reaction conditions and found that all
obtained chalcones are converted into the target quinolines
in high or excellent yields (Scheme 2, Table 1). The
slightly smaller (70%) yield of quinoline 5b compared with
the other products is probably due to the mesomeric effect
in the p-methoxy-substituted chalcone 3b, reducing the
positive charge on the carbonyl carbon atom that decreases
the reactivity of the carbonyl group. It should be noted that
the reaction proceeds in high yield even in the case of
enone 3e, with the formation of 2-thienylquinoline 5e.
The mechanism proposed for the cyclodehydration is an
acid-catalyzed (E,Z)-isomerization of compound (E)-3
leading to enone (Z)-3, which after rotation around the C–C
bond assumes the reaction conformation I6. Further
nucleophilic attack of the o-amino group on the carbonyl
carbon atom leads to the intermediate I7. Subsequent
aromatization via elimination of TsOH molecule, proceeding
either stepwise or in concerted way, completes the formation
of the desired quinoline 5 (Scheme 3).
According to density functional theory calculations
(B3LYP/6-31G, Supporting information file) the isomer
(E)-3a is by 5.4 kcal/mol lower in energy than isomer
(Z)-3a. The formation of the intermediate I6 (R1 = Ph)
requires additional 4.0 kcal/mol. Further steps are,
however, exothermic: the corresponding intermediate I7 is
2.9 kcal/mol more stable than intermediate I6. Elimination
of TsOH from intermediate I7 with the formation of
quinoline 5a occurs with the release of 15.9 kcal/mol.
Consequently, the formation of quinoline 5a from chalcone
In order to convert the obtained α,β-unsaturated ketones
3a–e to substituted quinolines, (E,Z)-isomerization is
necessary. We hypothesized that this process can be carried
out under acidic conditions, therefore, the next step of our
research was to find the optimal reaction conditions using
chalcone 3a as the model compound. By varying the
temperature and the amount of the acidic initiator we found
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Chemistry of Heterocyclic Compounds 2016, 52(12), 1087–1091
Scheme 3
CH2Cl2, 3:1). If necessary, the obtained product can be
recrystallized from a appropriate solvent mixture.
4-Methyl-N-{2-[(E)-3-oxo-3-phenylprop-1-en-1-yl]phe-
nyl}benzosulfamide (3а). Yield 490 mg (65%), white solid,
1
mp 175–176°С (CH2Cl2) (mp 176–178°С10a). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 2.05 (3H, s, CH3); 6.78
(1H, br. s, NH); 6.95–7.02 (2H, m, H Ar); 7.07 (1H, d,
3J = 15.5, =CH); 7.09–7.15 (1H, m, H Ar); 7.18–7.28 (1H,
m, H Ar); 7.31–7.38 (3H, m, H Ar); 7.40–7.47 (4H, m,
3
H Ar); 7.50 (1H, d, J = 15.5, =CH); 7.76–7.84 (2H, m,
H Ar). 13C NMR spectrum (CDCl3), δ, ppm: 21.5; 124.8;
127.2; 127.3; 127.4 (2C); 127.5; 128.7 (2C); 128.9 (2C);
129.9 (2C); 131.0; 131.2; 133.2; 135.4; 136.3; 137.9;
139.0; 144.1; 190.0.
N-{2-[(E)-(4-Methoxyphenyl)-3-oxoprop-1-en-1-yl]phe-
nyl}-4-methylbenzosulfamide (3b). Yield 570 mg (70%), pale-
yellow solid, mp 158–159°С (CH2Cl2) (mp 155–157°С10a).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.14 (3H, s,
CH3); 3.87 (3H, s, OCH3); 6.92–6.97 (2H, m, H Ar); 7.08–
(E)-3a is an exothermic process, which is fully consistent
with experimental data.
3
In conclusion, we have developed an efficient method
for the synthesis of quinolines from (E)-3-[(2-tosylamino)-
phenyl]-1-(het)arylprop-2-en-1-ones. The reaction takes
place as a result of acid-catalyzed cyclodehydration
comprising the key step of (E,Z)-isomerization, and leads
to the desired products in high yields. It should be noted
that, unlike the Friedlaender synthesis, the developed
method allows to isolate the intermediate 2-(tosylamino)-
chalcones which can be easily modified. These products
may be subjected to the subsequent cyclodehydration
reaction, thereby increasing the spectrum of the resulting
quinolines. The precursor chalcones were prepared by
condensation of 2-(tosylamino)benzaldehyde with readily
available ketones.
7.13 (2H, m, H Ar); 7.18 (1H, d, J = 15.4, =CH); 7.21–
7.27 (1H, m, H Ar); 7.33–7.40 (1H, m, H Ar); 7.46–7.54
(2H, m, H Ar); 7.54–7.61 (3H, m, H Ar, NH); 7.73 (1H, d,
3J = 15.4, =CH); 7.90–7.99 (2H, m, H Ar). 13C NMR
spectrum (CDCl3), δ, ppm: 21.4; 55.6; 114.1 (2С); 124.5;
127.2; 127.3; 127.4 (2С); 127.8; 129.8 (2С); 130.8; 131.0;
131.1 (2С); 131.3; 135.5; 136.3; 138.6; 143.9; 163.8; 188.4.
4-Methyl-N-{2-[(E)-(4-methylphenyl)-3-oxoprop-1-en-
1-yl]phenyl}benzosulfamide (3c). Yield 532 mg (68%),
white solid, mp 171–172 °С (CH2Cl2) (mp 171–172°С10a).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.13 (3H, s,
CH3); 2.40 (3H, s, CH3); 7.06–7.11 (2H, m, H Ar); 7.17
3
(1H, d, J = 15.4, =CH); 7.21–7.28 (3H, m, H Ar); 7.33–
7.39 (1H, m, H Ar); 7.45–7.50 (3H, m, H Ar, NH); 7.53–
7.59 (2H, m, H Ar); 7.72 (1H, d, 3J = 15.4, =CH); 7.80–7.86
13
Experimental
(2H, m, H Ar). C NMR spectrum (CDCl3), δ, ppm: 21.4;
IR spectra were registered on an FSM-1202
spectrometer in petroleum jelly. 1H and 13C NMR spectra were
acquired on a Bruker Avance III HD 400 spectrometer (400 and
100 MHz, respectively) at room temperature in CDCl3 or
DMSO-d6. Chemical shifts were assigned relative to the signal
of the solvent (CDCl3 – 7.26 ppm, DMSO-d6 – 2.50 ppm) or
the central component of the solvent signal (for 13С nuclei:
CDCl3 – 77.16 ppm, DMSO-d6 – 39.52 ppm). Melting
points were determined on a Stuart SMP30 apparatus.
Elemental analysis was performed on a varioMICROcube
CHNS-analyzer. TLC was performed on Sorbfil plates.
Machery Nagel (40–63 m) silica gel was used for
chromatographic purification.
Synthesis of compounds 3а–е (General method). 40%
Aqueous KOH solution (5 ml) was added dropwise to a solu-
tion of 2-(tosylamino)benzaldehyde (1) (550 mg, 2 mmol)
and ketone 2a–e (2 mmol) in EtOH (30 ml) at 40°C. The
reaction mixture was stirred for 5 h, then poured into water
(200 ml), and the mixture was extracted with ethyl acetate
(3×30 ml). The combined organic fractions were washed
with saturated aqueous NH4Cl (3×10 ml), followed by
water (3×30 ml), saturated aqueous NaCl (3×10 ml), and
dried with anhydrous Na2SO4. The product was separated
by column chromatography (eluent petroleum ether–
21.8; 124.6; 127.2; 127.3; 127.4 (2С); 127.9; 128.9 (2С);
129.5 (2С); 129.8 (2С); 131.1; 131.3; 135.3; 135.5; 136.3;
139.0; 143.9; 144.1; 189.7.
N-{2-[(E)-(4-Fluorophenyl)-3-oxoprop-1-en-1-yl]phe-
nyl}-4-methylbenzosulfamide (3d). Yield 442 mg (56%),
white solid, mp 206–207°С (EtOH–1,4-dioxane). IR spectrum,
1
ν, cm–1: 3194, 1655, 1599, 1333, 1269, 1155. H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 2.19 (3H, s, CH3);
6.99–7.05 (1H, m, H Ar); 7.21–7.28 (2H, m, H Ar);
7.29–7.43 (4H, m, H Ar); 7.45–7.53 (2H, m, H Ar); 7.61
(1H, d, 3J = 15.4, =CH); 7.87 (1H, d, 3J = 15.4, =CH); 7.97–
8.03 (1H, m, H Ar); 8.14–8.22 (2H, m, H Ar); 9.97 (1H, s,
NH). 13C NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 20.7;
115.6 (2C, d, 2JCF = 21.8); 122.7; 126.6 (2C); 127.0; 127.5;
3
127.8; 129.5 (2C); 130.8; 131.3 (2C, d, JCF = 9.4); 131.9;
4
134.2 (d, JCF = 2.5); 135.8; 136.7; 139.7; 142.9; 164.9 (d,
1JCF = 251.3); 187.6. Found, %: С 66.87; H 4.71; N 3.34.
C22H18FNO3S. Calculated, %: С 66.82; H 4.59; N 3.54.
4-Methyl-N-{2-[(E)-3-oxo-3-(thiophen-2-yl)prop-1-en-
1-yl]phenyl}benzosulfamide (3e). Yield 452 mg (59%),
white solid, mp 202–203°С (EtOH–1,4-dioxane). IR spectrum,
1
ν, cm–1: 3269, 1653, 1595, 1328, 1273, 1159. H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 2.19 (3H, s, CH3);
6.99–7.06 (1H, m, H Ar); 7.22–7.28 (2H, m, H Ar); 7.23–
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Chemistry of Heterocyclic Compounds 2016, 52(12), 1087–1091
7.29 (1H, m, H thiophene); 7.32–7.36 (1H, m, H Ar); 7.36–
(1H, m, H Ar); 7.81–7.85 (1H, m, H Ar); 7.88 (1H, d,
3J = 8.7, H Ar); 8.08–8.16 (2H, m, H Ar); 8.21 (1H, d,
3J = 8.7, H Ar); 8.21–8.23 (1H, m, H Ar). 13C NMR
spectrum (CDCl3), δ, ppm: 21.4; 118.9; 126.2; 127.3;
127.5; 127.6 (2С); 129.7 (3С); 129.8; 136.8; 137.0; 139.6;
148.4; 157.4.
7.39 (1H, m, H thiophene); 7.46–7.51 (2H, m, H Ar); 7.54
(1H, d, 3J = 15.4, =CH); 7.86 (1H, d, 3J = 15.4, =CH); 7.95–
8.00 (1H, m, H Ar); 8.02–8.07 (1H, m, H Ar); 8.17–8.23
13
(1H, m, H thiophene); 9.99 (1H, s, NH). C NMR spectrum
(DMSO-d6), δ, ppm: 20.6; 122.8; 126.6 (2C); 127.0; 127.4;
127.8; 128.7; 129.5 (2C); 130.8; 131.8; 133.3; 135.2;
135.8; 136.6; 138.7; 143.0; 145.3; 181.3. Found, %:
С 62.46; H 4.45; N 3.72. C20H17NO3S2. Calculated, %:
С 62.64; H 4.47; N 3.65.
2-(4-Fluorophenyl)quinoline (5d). Yield 106 mg (95%),
white solid, mp 93–94°С (mp 91–93°С10b). 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.18–7.25 (2H, m,
H Ar); 7.49–7.58 (1H, m, H Ar); 7.69–7.78 (1H, m, H Ar);
7.78–7.87 (2H, m, H Ar); 8.09–8.28 (4H, m, H Ar).
13C NMR spectrum (CDCl3), δ, ppm (J, Hz): 115.9 (2С, d,
2JCF = 21.6); 118.7; 126.5; 127.3; 127.6; 129.6 (2С, d,
N-[2-(1,5-Dioxo-1,5-diphenylpentan-3-yl)phenyl]-
4-methylbenzosulfamide (4а). Yield 109 mg (11%),
colorless transparent needles, mp 235–236°С (CH2Cl2).
IR spectrum, ν, cm–1: 3290, 1678, 1666, 1597, 1335, 1240,
1167. 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.67 (3H,
s, CH3); 2.61 (2H, dd, 2J = 18.4, 3J = 6.4, СH2); 3.33 (2H, dd,
4
3JCF = 8.4); 129.8; 129.9; 136.0 (d, JCF = 2.4); 137.1;
148.4; 156.4; 164.0 (d, 1JCF = 249.3).
2-(Thiophen-2-yl)quinoline (5e). Yield 92 mg (87%),
2J = 18.4, J = 6.4, СH2); 3.62–3.99 (1H, m, СH); 6.84–
white solid, mp 132–133°С (mp 127–128°С10b). H NMR
3
1
6.97 (2H, m, H Ar); 7.09–7.16 (1H, m, H Ar); 7.16–7.25
(2H, m, H Ar); 7.38–7.48 (4H, m, H Ar); 7.52–7.59 (4H,
m, H Ar); 7.60–7.68 (1H, m, H Ar); 7.78–7.92 (4H, m,
H Ar); 8.77 (1H, s, NH). 13C NMR spectrum (CDCl3), δ,
ppm: 20.7; 28.4; 45.1 (2C); 127.1; 127.3; 127.5 (2C);
127.6; 128.2 (4C); 128.6; 128.8 (4C); 129.6 (2C); 133.6
(2C); 134.2; 136.5 (2C); 137.5; 139.7; 143.2; 198.4 (2C).
Found, %: С 72.56; H 5.21; N 2.68. C30H27NO4S.
Calculated, %: С 72.41; H 5.47; N 2.81.
spectrum (CDCl3), δ, ppm (J, Hz): 7.11–7.20 (1H, m,
H thiophene); 7.43–7.51 (2H, m, H thiophene, H Ar); 7.63–
7.85 (4H, m, H thiophene, H Ar); 8.07–8.15 (2H, m, H Ar).
13C NMR spectrum (CDCl3), δ, ppm: 117.8; 126.0; 126.2;
127.4; 127.6; 128.2; 128.7; 129.5; 129.9; 136.7; 145.5;
148.3; 152.5.
1
The Supporting information file containing Н and 13С
NMR spectra of the synthesized compounds and the results
of the calculations of the intermediates in the synthesis of
compound 5а by В3LYP/6-31G is available at http://
link.springer.com/journal/10593.
Synthesis of compounds 5a–e (General method). TfOH
(133 ml, 1.5 mmol) was added to a solution of enone 3a–e
(0.5 mmol) in 1,2-dichloroethane (0.5 ml). The reaction
mixture was stirred at 85°С for 12 h, then after cooling
10% aqueous NaOH solution was added dropwise. The
organic layer was separated, and the aqueous phase
extracted with CH2Cl2 (2×2 ml). The combined organic
fractions were washed with water (3×3 ml), followed by
saturated aqueous NaCl (3×3 ml), and dried with anhydrous
Na2SO4. The product was isolated by column
chromatography (eluent petroleum ether–CH2Cl2, 4:1). If
necessary, the obtained product can be recrystallized from
a petroleum ether–CH2Cl2 mixture.
This work was supported by the Russian Foundation for
Basic Research (grant 16-03-00513 А) and the Ministry of
Education and Science of the Russian Federation (state
assignment № 4.246.2014/K).
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2-Phenylquinoline (5а). Yield 92 mg (90%), white
1
solid, mp 84–85°С (mp 84–86°С10b). H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 7.42–7.61 (4H, m, H Ar); 7.69–
7.77 (1H, m, H Ar); 7.82 (1H, d, 3J = 8.4, H Ar); 7.87 (1H,
3
d, J = 8.4, H Ar); 8.11–8.28 (4H, m, H Ar). 13C NMR
spectrum (CDCl3), δ, ppm: 119.1; 126.4; 127.4; 127.6;
127.7 (2С); 128.9 (2С); 129.4; 129.8; 129.9; 136.9; 139.8;
148.5; 157.5.
2-(4-Metoxyphenyl)quinoline (5b). Yield 82 mg (70%),
1
white solid, mp 123–124°С (mp 121–124°С10b). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 3.89 (3H, s, OCH3);
7.00–7.11 (2H, m, H Ar); 7.46–7.54 (1H, m, H Ar); 7.67–
7.74 (1H, m, H Ar); 7.76–7.86 (2H, m, H Ar); 8.13–8.20
(4H, m, H Ar). 13C NMR spectrum (CDCl3), δ, ppm: 54.8;
113.7 (2С); 117.9; 125.3; 126.4; 126.8; 128.4 (2С); 128.9;
129.0; 131.6; 136.1; 147.7; 156.3; 160.4.
2-(4-Methylphenyl)quinoline (5c). Yield 105 mg (96%),
1
pale-beige solid, mp 81–82°С (mp 82–83°С10b). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 2.47 (3H, s, CH3); 7.32–
7.40 (2H, m, H Ar); 7.50–7.57 (1H, m, H Ar); 7.71–7.79
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