Quinolines synthesis by reacting 1,3-butanediol with anilines in the presence of iron catalysts

Article abstract of DOI:10.1134/S1070363216070136

2-, 4-, 6-, 7-, and 8-substituted quinolines were synthesized in 78–95% yield by the reaction of 1,3- butanediol with anilines in the presence of iron catalysts in carbon tetrachloride.

Full text of DOI:10.1134/S1070363216070136

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 7, pp. 1613–1618. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © R.I. Khusnutdinov, A.R. Bayguzina, R.I. Aminov, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 7, pp. 1135–1140.
Quinolines Synthesis by Reacting 1,3-Butanediol with Anilines
in the Presence of Iron Catalysts
R. I. Khusnutdinov, A. R. Bayguzina, and R. I. Aminov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, pr. Oktyabrya 141, Ufa, 450075 Russia
e-mail: khusnutdinovri47@gmail.com
Received December 30, 2016
Abstract—2-, 4-, 6-, 7-, and 8-substituted quinolines were synthesized in 78–95% yield by the reaction of 1,3-
butanediol with anilines in the presence of iron catalysts in carbon tetrachloride.
Keywords: cyclocondensation, anilines, 1,3-butanediol, carbon tetrachloride, quinolines, metal complex catalysis
DOI: 10.1134/S1070363216070136
Quinoline and its derivatives are important
synthons in the preparation of inhibitors of acid
corrosion of metals, extractants, sorbents, and cyanine
dyes. Some effective antimalarial, antibacterial, and
anti-tremor medications consisted of quinoline deriva-
tives. General methods for the synthesis of quinolines
are based on cyclocondensation of anilines with
oxygen-containing compounds like glycerol, α,β-
unsaturated aldehydes, β-diketones, and β-ketoesters in
the presence of mineral acids [1–4].
presence of ruthenium complexes the final stage of
aromatization does not require the use of hydrogen
acceptors, since the catalyst performs this role.
Previously we have found that synthesis of quinolines
can be carried out by reacting anilines with propane-
1,3-diol in the presence of Fe-containing catalysts [7].
Here we report on the synthesis of quinolines by
reacting 1,3-butanediol with anilines 1a–1j in the
presence of iron-containing catalysts like FeCl3·6H2O,
FeCl3, FeCl2·4H2O, Fe(C5H5)2, Fe(acac)3, Fe(OAc)2,
Fe2(CO)9, the best of which was FeCl3·6H2O.
In recent years new methods of quinolines pre-
paration in the absence of acids using metal complex
catalysts were developed. They allowed a significant
expansion of the range of C3-substrates used for
constructing quinoline ring involving anilines and 1,3-
diols.
Thus, cyclocondensation of aniline 1a with 1,3-
butanediol produced a difficulty separable mixture of
4-methyl- (2a) and 2-methylquinolines (3a) with a
predominance of the 4-substituted isomer. The reaction
took place at 150°C in CCl4 within 8 hours at a molar
ratio FeCl3·6H2O : 1а : СCl4 : 1,3-butanediol = 1 :
100 : 200 : 400. Substituted anilines 1b–1j reacted
with 1,3-butanediol similarly to form substituted
quinolines 2 and 3 in 78–95% yields (see table,
Scheme 1).
Synthesis of quinolines starting from anilines and
1,3-diols have been successfully carried out in the
presence of ruthenium-containing catalysts RuCl3·
nH2O–PBu3 and RuCl3·nH2O–PEt3 when refluxed in
diglyme for 5 h [5, 6]. It should be noted that in the
Scheme 1.
Me
N
Me
FeCl3 6H2O
HO
X
+
X
+ X
CCl4, 150оС, 8 h
N
Me
NH2
HO
78_95%
3
1
2
X = H (a), o-CH3 (b), m-CH3 (c), p-CH3 (d), o-C2H5 (e), o-Cl (f), m-Cl (g), p-Cl (h), p-OCH3 (i), o-OH (j).
1613

1614
KHUSNUTDINOV et al.
Synthesis of quinolines by reacting anilines with 1,3-butane-
diol in the presence of FeCl3·6H2Oa
It has been previously found [8] that the reaction of
aniline with 1,3-diol in the presence of Ru-containing
catalyst occurred via initial oxidation of diol into 3-
hydroxybutanal A, which suffered a dehydrogenation
to afford crotonaldehyde E. In our case, due to the
known [7] ability of both hydroxy groups to be
oxidized with CCl4 by the action of iron compounds it
was expectable to obtain 3-hydroxybutanal A and 4-
Aniline
1а
Isomer ratio 2 : 3b
Yield, %
95
2 : 1
1b
1c
2 : 1
80
3 : 2 : 1
1 : 1
78
1d
1e
93
hydroxybutane-2-one
B
through generating two
2 : 1
87
alkylhypochlorites C and D. The degradation of
hypochlorites C and D with the release of HCl yielded
aldehydes A and B, which may undergo dehydration to
form crotonaldehyde E and methyl vinyl ketone F.
Compounds A, B and F reacted further with aniline to
give the corresponding intermediates G and H [8]. Due
to differences in the structure compounds A, B and F
reacted with aniline in two directions: compound A
provided a Schiff base, intermediate B alkylated
aniline at the amino group, and compound F reacted
1f
3 : 1
94
1g
3 : 2 : 1
2 : 1
79
1h
1i
82
1 : 1
89
1j
1 : 1
90
a
Reaction conditions: 150°C, 8 h, FeCl3·6H2O : 1 : CCl4 : diol =
1 : 100 : 200 : 400. b The isomers ratio was determined by NMR
spectroscopy.
Scheme 2.
HO
Me
OH
[Fe] _ CCl4
_CHCl3
Me
OCl
Me
OH
HO
ClO
D
C
_HCl
_HCl
c
d
e
O
Me
Me
OH
Me
O
HO
Me
_H2O
_H2O
O
O
E
A
B
F
[Fe], PhNH2
_H2O
[Fe], PhNH2
_H2O
_H2O
[Fe], PhNH2
[Fe], PhNH2
а
b
Me
HO
Me
O
Me
O
Me
N
H
N
N
N
G
H
_H2O
_H2
_H2O
_H2
H
_H2
_H2O
_H2
Me
2a
2a
N
N
Me
3a
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

QUINOLINES SYNTHESIS BY REACTING 1,3-BUTANEDIOL WITH ANILINES
1615
Scheme 3.
CH3
O
FeCl3 6H2O
+
110оС, 8 h
N
NH2
F
2a (87%)
1a
spectra were obtained on a Shimadzu GCMS-
QP2010Plus spectrometer (capillary column SPB-5,
30 mm × 0.25 mm, carrier gas helium, programming
temperature from 40 to 300°C at a rate of 8 deg/min,
evaporation temperature 280°C, temperature of ion
source 200°C, ionization energy 70 eV). GLC analysis
was performed on Shimadzu GC-9A, GC-2014 instru-
ments [column 2 m × 3 mm, stationary phase Silicone
SE-30 (5%) on Chromaton N-AW-HMDS, ramp from
50 to 270°C C, heating rate 8 deg/min, carrier gas
helium (47 mL/min)]. High performance liquid chro-
matographic analysis was carried out under the
following conditions: column 250 mm × 10 mm,
Zorbax ODS, 5 μm, eluent CH3CN : H2O = 70 : 30,
0.1% (C2H5)3N, 3 mL/min, detector SPD-20A, λ = 265 nm.
with aniline by Michael reaction. Intermediates G and
H underwent heterocyclization, dehydration and dehyd-
rogenation to give 4-methylquinoline 2a (routes c and
d) (Scheme 2).
The formation of 2-methylquinoline 3a is only
possible by Michael reaction (route b) involving croton-
aldehyde D. The latter can react with aniline to form a
Schiff base (route a) providing compound 2a. The
formation of 4-methylquinoline 2a is possible by four
pathways causing probably its prevalence in the
reaction products.
Furthermore, the proposed mechanism is proved by
the formation of stoichiometric amount of chloroform
and HCl, which were detected by GLC and mer-
curimetric titration. A control experiment with methyl
vinyl ketone F led to the selective production of 4-
methylquinoline 2a, which also confirms the proposed
reaction mechanism, providing for the formation of
intermediate H.
Commercially available anilines, 1,3-butanediol,
and carbon tetrachloride were distilled before use. Iron
catalysts [FeCl3·6H2O, FeCl3, FeCl2·4H2O, Fe(C5H5)2,
Fe(acac)3, Fe(OAc)2, Fe2(CO)9] were used as
purchased without further purification.
It should be noted that the reaction of aniline with
methyl vinyl ketone was carried out at a lower tem-
perature, since under standard conditions (150°C, 8.4 h)
it underwent polymerization. It was found that in the
absence of FeCl3·6H2O there was no reaction between
aniline and methyl vinyl ketone. Apparently, a catalyst
role in the quinolines formation from anilines and diols
is not limited to the participation in 1,3-diols oxidation
(Scheme 3).
General procedure for preparation of sub-
stituted quinolines 2 and 3. A vial charged with
0.02 mmol of FeCl3·6H2O [FeCl3, FeCl2·4H2O,
Fe(C5H5)2, Fe(acac)3, Fe(OAc)2, Fe2(CO)9], 2 mmol of
aniline 1, 4 mmol of carbon tetrachloride and 8 mmol
of 1,3-diol under argon was sealed, placed into a
pressure reactor, and heated at 150°C with stirring for
8 h. After the reaction completed the mixture was
dissolved in hydrochloric acid, and separated. The
aqueous layer was neutralized with 10% sodium
hydroxide and extracted with methylene chloride. The
organic layer was filtered and evaporated. The residue
was distilled in a vacuum. Analytically pure samples
were isolated by semi-preparative HPLC. Physical and
chemical constants and spectral characteristics cor-
responded to those reported in [5, 6, 8–22].
In summary, a convenient method for the synthesis
of 2-, 4-, 6-, 7-, and 8-substituted quinolines was de-
veloped based on the reaction of aniline and its
derivatives with 1,3-butanediol catalyzed with FeCl3·
6H2O in the presence of CCl4. The latter takes part in
1,3-butanediol oxidation, converting it into a carbonyl
compound.
4-Methylquinoline (2a). bp 80–81°C (2 mmHg).
1Н NMR spectrum (СDCl3), δ, ppm: 2.68 s (3H, CH3),
7.18 d (1H, С3H, J = 8.0 Hz), 7.53 t (1H, С6H, J =
7.6 Hz), 7.68 t (1H, С7H, J = 7.6 Hz), 7.95 d (1H, С5H,
J = 9.2 Hz), 8.09 d (1H, С8H, J = 8.4 Hz), 8.73 d (1H,
EXPERIMENTAL
1H and 13C NMR spectra were recorded on a Bruker
Avance-400 spectrometer (400.13 and 100.62 MHz,
respectively) in CDCl3, internal reference TMS. Mass
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

1616
KHUSNUTDINOV et al.
С2H, J = 8.4 Hz). 13С NMR spectrum, δС, ppm: 18.40
(СН3), 121.87 (C3), 123.85 (C5), 126.33 (C6), 127.99
(C4а), 128.95 (C7), 129.76 (C8), 144.50 (C4), 147.76
(C8a), 150.01 (C2). Mass spectrum, m/z (Irel, %): 143.18
(100) [M – H]+, 128 (34), 115 (19), 101 (8), 89 (5), 75
(4), 51(4).
(1H, С6H), 7.58 d (1H, С7H, J = 7.6 Hz), 7.84 d (1H,
С5H, J = 8.4 Hz), 8.80 m (1H, С2H). 13С NMR spec-
trum, δС, ppm: 18.98 (СН3), 121.68 (C3), 125.41 (C6),
126.41 (C4а), 127.71 (C7), 127.65 (C5), 142.30 (C8),
143.28 (C4), 144.53 (C8a), 148.84 (C2). Mass spectrum,
m/z (Irel, %): 177. 1 [M – H]+, 142 (14), 115 (15), 76 (7).
4,8-Dimethylquinoline
(2b).
bp
65–66°C
4-Methyl-7-chloroquinoline (2g). bp 92–93°C
(0.3 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.75
s (3H, CH3), 7.10–7.20 m (1H, С3H), 7.30–7.55 m
(1H, С6H), 7.70–8.00 m (1H, С5H), 8.07 s (1H, С8H),
8.60–8.78 m (1H, С2H). 13С NMR spectrum, δС, ppm:
18.55 (СН3), 122.04 (C3), 125.23 (C6), 127.82 (C4а),
130.25 (C5), 127.16 (C8), 134.90 (C7), 144.40 (C4),
150.19 (C8a), 151.14 (C2). Mass spectrum, m/z (Irel, %):
177 (100) [M – H]+, 179 (34), 178 (10), 143 (12), 115
(19), 76 (9).
(0.3 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.79
s (3H, CH3), 2.89 s (3H, CH3), 7.15–7.30 m (1H, С3H),
7.47 t (1H, С6H, J = 7.2 Hz), 7.50–7.65 m (1H, C7),
7.86 d (1H, С5H, J = 8.4 Hz), 8.84 d (1H, С2H, J =
7.6 Hz). 13С NMR spectrum, δС, ppm: 18.91 (СН3),
18.94 (СН3), 121.79 (C3), 125.55 (C6), 126.07 (C5),
129.42 (C7), 136.26 (C8), 139.45 (C4а), 148.84 (C4),
147.00 (C8a), 148.94 (C2). Mass spectrum, m/z (Irel, %):
157.00 (100) [M – H]+, 156 (31), 143 (10), 115 (8),
71 (4), 65 (2), 52 (2).
4-Methyl-6-chloroquinoline (2h). bp 100–101°C
(0.5 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.69
s (3H, CH3), 7.25 d (1H, С3H, J = 7.6 Hz), 7.72 d (1H,
С7H, J = 7.6 Hz), 7.72 s (1H, С5H), 8.10 d (1H, С8H,
J = 8.4 Hz), 8.76 d (1H, С2H, J = 8 Hz). 13С NMR
spectrum, δС, ppm: 18.57 (СН3), 122.85 (C3), 135.10
(C6), 127.05 (C4а), 126.11 (C5), 122.85 (C8), 130.26
(C7), 143.93 (C4), 145.86 (C8a), 150.07 (C2). Mass
spectrum, m/z (Irel, %): 177 (100) [M – H]+, 179 (42),
142 (51), 116 (27), 99 (14), 51 (27).
1
4,7-Dimethylquinoline (2c). Н NMR spectrum
(СDCl3), δ, ppm: 2.54 s (3H, CH3), 2.64 s (3H, CH3),
7.14 d (1H, С3H, J = 7.2 Hz), 7.38 d (1H, C8H, J =
6.8 Hz), 7.85–7.95 m (1H, С5,6H), 8.71 d (1H, С2H, J =
8.0 Hz). 13С NMR spectrum, δС, ppm: 18.61 (СН3),
21.72 (СН3), 121.13 (C3), 123.56 (C6), 126.34 (C5),
128.56 (C4а), 128.82 (C8), 139.3 (C7), 144.15 (C4),
148.10 (C8a), 150.04 (C2).
4,6-Dimethylquinoline (2d).1Н NMR spectrum
(СDCl3), δ, ppm: 2.59 s (3H, CH3), 2.69 s (3H, CH3),
7.16 d (1H, С3H, J = 8.0 Hz), 7.52 d (1H, С7H, J =
8.4 Hz), 7.72 s (1H, С5H), 7.99 d (1H, С8H, J = 8.4 Hz),
8.69 d (1H, С2H, J = 7.6 Hz). 13С NMR spectrum, δС,
ppm: 18.61 (СН3), 21.80 (CH3), 121.81 (C3), 122.75
(C5), 128.20 (C4а), 129.60 (C8), 131.34 (C7), 136.02
(C4), 143.53 (C6), 146.46 (C8a), 149.21 (C2). Mass
spectrum, m/z (Irel, %): 158.00 (100) [M – H]+.
4-Methyl-6-methoxyquinoline (2i). mp 26–29°C.
1Н NMR spectrum (СDCl3), δ, ppm: 2.63 s (3H, CH3),
3.94 s (3H, OCH3), 7.15–7.18 m (2H, С3,5H), 7.35 d
(1H, С7H, J = 7.6 Hz), 8.00 d (1H, С8H, J = 8.4 Hz),
8.61 d (1H, С2H, J = 8.8 Hz). 13С NMR spectrum, δС,
ppm: 18.80 (СН3), 55.53 (OCH3), 101.9 (C5), 121.47
(C7), 122.15 (C3), 129.25 (C4а), 131.46 (C4), 142.73
(C8), 144.01 (C8a), 147.67 (C2), 157.60 (C6).
4-Methyl-8-ethylquinoline (2e). bp 73–74°C
(0.2 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 1.30–
1.60 m (3H, CH3), 2.68 s (3Н, CH3), 3.30–3.50 m (2Н,
CH2), 7.51 t (1H, С6H, J = 7.6 Hz), 7.60 d (1H, С7H,
J = 7.6 Hz), 7.86 d (1H, С5H, J = 8.4 Hz), 7.99 s (1H,
С4H). 13С NMR spectrum, δС, ppm: 15.22 (СH2CH3),
25.00 (СH2CH3), 18.97 (CH3), 121.79 (C3), 125.39
(C5), 126.03 (C6), 126.43 (C4а), 127.67 (C7), 136.22
(C8), 143.40 (C4), 144.36 (C8a), 148.91 (C2). Mass
spectrum, m/z (Irel, %): 170.10 (100) [M – H]+, 171
(83), 143 (63), 128 (16), 115 (36), 63 (40), 51 (50).
4-Methyl-8-hydroxyquinoline (2j). bp 65–66°C
(0.2 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.68
s (3H, CH3), 7.12–7.28 m (2H, С3,5H), 7.43–7.45 m
(2H, С6,7H), 8.61 d (1H, С2H, J = 8.4 Hz). 13С NMR
spectrum, δС, ppm: 18.72 (СН3), 109.68 (C7), 114.87
(C5), 122.46 (C3), 127.2 (C4a), 128.41 (C6), 138.04
(C4), 145.00 (C8a), 147.30 (C8), 152.57 (C2). Mass
spectrum, m/z (Irel, %): 159 (100) [M – H]+, 160 (12),
131 (77).
2-Methylquinoline (3a). bp 80–81°C (2 mmHg).
1Н NMR spectrum (СDCl3), δ, ppm: 2.78 s (3H, CH3),
7.22 d (1H, С3H, J = 8.0 Hz), 7.68 t (1H, С7H, J =
4.0 Hz), 7.46 t (1H, С6H, J = 6.4 Hz), 7.73 d (1H, С5H,
J = 9.2 Hz), 7.91 d (1H, С4H, J = 9.2 Hz), 7.91 d (1H,
4-Methyl-8-chloroquinoline (2f). bp 87–89°C
(0.2 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.68
s (3H, CH3), 7.20–7.40 m (1H, С3H), 7.45–7.60 m
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

QUINOLINES SYNTHESIS BY REACTING 1,3-BUTANEDIOL WITH ANILINES
1617
С8H, J = 9.2 Hz). 13С NMR spectrum, δС, ppm: 25.12
(СН3), 121.74 (C3), 125.45 (C6), 126.32 (C4а), 127.37
(C5), 128.80 (C8), 129.19 (C7), 135.84 (C4), 147.76
(C8a), 158.67 (C2). Mass spectrum, m/z (Irel, %): 143.18
(100) [M – H]+, 128 (20), 115 (22), 101 (5), 89 (4),
75 (5), 51(4).
2-Methyl-8-chloroquinoline (3g). mp 65–68°C. 1Н
NMR spectrum (СDCl3), δ, ppm: 2.84 s (3H, CH3),
7.38–7.50 m (1H, С3,6H), 7.82 d (1H, С7H, J = 7.6 Hz),
8.00 d (1H, С4H, J = 8.4 Hz), 8.03 d (1H, С5H, J =
8 Hz). 13С NMR spectrum, δС, ppm: 25.19 (СН3), 122.84
(C3), 125.45(C6), 126.32 (C4а), 127.37 (C5), 128.80
(C7), 130.13 (C8), 137.89 (C4), 148.56 (C8a), 161.87
(C2). Mass spectrum, m/z (Irel, %): 177. 1 [M – H]+.
2,8-Dimethylquinoline
(3b).
bp
65–66°C
(0.3 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.65
s (3H, CH3), 2.87 s (3H, CH3), 6.98 d (1H, С5H, J =
8.0 Hz), 7.24 d (1H, С3H, J = 8.4 Hz), 7.38 t (1H, С6H,
J = 8.0 Hz), 7.65 d (1H, С7H, J = 8.0 Hz), 7.89 d (1H,
С4H, J = 7.6 Hz). 13С NMR spectrum, δС, ppm: 21.56
(СН3), 25.67 (СН3), 121.63 (C3), 125.29 (C5), 126.98
(C6), 127.33 (C4а), 128.26 (C7), 136.50 (C8), 137.49
(C4), 144.67 (C8a), 157.85 (C2). Mass spectrum, m/z
(Irel, %): 157.00 (100) [M – H]+, 156 (31), 143 (10),
115 (8), 71 (4), 65 (2), 52 (2).
2-Methyl-7-chloroquinoline (3h). bp 70–71°C
(0.2 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.63
s (3H, CH3), 7.12 d (1H, С3H, J = 7.6 Hz), 7.25 d (1H,
С6H, J = 7.6 Hz), 7.48 d (1H, С5H, J = 9.2 Hz), 7.84 d
(1H, С4H, J = 8.4 Hz), 7.93 s (1H, С8H). 13С NMR
spectrum, δС, ppm: 25.38 (СН3), 122.17 (C3), 124.89
(C6), 126.69 (C4а), 124.86 (C5), 127.85 (C8), 135.11
(C7), 135.84 (C4), 148.36 (C8a), 159.99 (C2). Mass
spectrum, m/z (Irel, %): 177 (100) [M – H]+, 179 (32),
178 (12), 142 (16), 115 (15), 76 (6).
2,7-Dimethylquinoline
(3c).
bp
53–54°C
1
(0.25 mmHg). Н NMR spectrum (СDCl3), δ, ppm:
2.40 s (3H, CH3), 2.64 s (3H, CH3), 7.00 d (1H, С5H,
J = 8.0 Hz), 7.03 d (1H, С6H, J = 8.0 Hz), 7.47 d (1H,
С4H, J = 7.6 Hz), 7.78 d (1H, С3H, J = 8.4 Hz), 7.79 s
(1H, С8H). 13С NMR spectrum, δС, ppm: 21.78 (СН3),
25.29 (СН3), 121.00 (C3), 124.48 (C5), 127.03 (C4а),
127.78 (C8), 127.81 (C7), 135.65 (C6), 139.40 (C4),
148.26 (C8a), 158.71 (C2). Mass spectrum, m/z (Irel, %):
157.00 (100) [M – H]+, 156 (28), 142 (11), 115 (11),
89 (4), 65 (4), 51 (4).
1
2-Methyl-5-chloroquinoline (3i). Н NMR spec-
trum (СDCl3), δ, ppm: 2.66 s (3H, CH3), 7.11 d (1H,
С3H, J = 7.6 Hz), 7.24 d (1H, С6H, J = 7.6 Hz), 7.45 t
(1H, С7H, J = 8.4 Hz), 7.84 d (1H, С4H, J = 8 Hz),
8.20 d (1H, С8H, J = 7.6 Hz). 13С NMR spectrum, δС,
ppm: 25.38 (СН3), 122.82 (C3), 124.96 (C6), 126.63
(C8), 126.69 (C4а), 130.08 (C7), 132.85 (C4), 134.88
(C5), 148.14 (C8a), 159.80 (C2).
1
2-Methyl-6-chloroquinoline (3j). mp 94–96°C. Н
NMR spectrum (СDCl3), δ, ppm: 2.69 s (3H,CH3),
7.28 d (1H, С3H, J = 7.6 Hz), 7.60 d (1H, С7H, J =
7.6 Hz), 7.73 s (1H, С5H), 7.91 d (1H, С8H, J = 8.4 Hz)
8.03 d (1H, С4H, J = 7.6 Hz). 13С NMR spectrum, δС,
ppm: 25.30 (СН3), 122.89 (C3), 135.21 (C6), 128.99
(C4а), 126.41 (C5), 122.89 (C8), 130.16 (C7), 135.21
(C4), 145.55 (C8a), 159.01 (C2). Mass spectrum, m/z
(Irel, %): 177 (100) [M – H]+, 179 (47), 142 (48), 116
(27), 99 (24), 51 (23).
2,6-Dimethylquinoline
(3e).
bp
75–76°C
(0.4 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.54
s (3H, CH3), 2.72 s (CH3), 7.21 d (1H, С3H, J =
8.0 Hz), 7.59 d (1H, С7H, J = 8.4 Hz), 7.73 s (1H,
С5H), 7.95 d (1H, С4H, J = 7.2 Hz), 7.93 d (1H, С8H,
J = 8.4 Hz). 13С NMR spectrum, δС, ppm: 21.36 (СН3),
25.13 (СН3), 121.78 (C3), 126.37 (C5), 126.42 (C4а),
128.35 (C8), 131.50 (C7), 135.19 (C6), 135.41 (C4),
146.76 (C8a), 157.84 (C2). Mass spectrum, m/z (Irel, %):
157.00 (100) [M – H]+, 156 (32), 142 (8), 115 (8), 89
(3), 77 (3), 65 (3).
2-Methyl-6-methoxyquinoline (3k). bp 95–96°C
(0.4 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.69
s (3H, CH3), 3.76 s (3H, OCH3), 6.89 d (1H, С3H, J =
8.0 Hz), 7.48 d (1H, С7H, J = 7.6 Hz), 7.63 s (1H,
С5H), 7.71 d (1H, С4H, J = 8.4 Hz), 7.91 d (1H, С8H,
J = 9.2 Hz). 13С NMR spectrum, δС, ppm: 24.85 (CH3),
55.42 (OCH3), 121.71 (C3), 122.01 (C6), 127.32 (C4а),
129.89 (C7), 134.78 (C4), 143.67 (C5), 155.49 (C8а),
157.45(C2). Mass spectrum, m/z (Irel, %): 173 (100)
[M – H]+, 158 (38), 130 (80), 103 (23), 77 (23).
2-Methyl-8-ethylquinoline (3f). bp 73–74°C
(0.2 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 1.30–
1.60 m (3H, CH3), 2.78 s (3Н, CH3), 3.30–3.50 m (2Н,
CH2), 7.43 t (1H, С6H, J = 7.2 Hz), 7.56 d (1H, С7H,
J = 6.8 Hz), 7.55–7.68 m (1H, С5H), 7.99 s (1H, С4H).
13С NMR spectrum, δС, ppm: 15.15 (СH2CH3), 24.34
(СH2CH3), 25.68 (CH3), 121.82 (C3), 125.43 (C5),
126.07 (C6), 126.24 (C4а), 128.34 (C7), 136.15 (C8),
142.38 (C4), 146.47 (C8a), 157.65 (C2). Mass spectrum,
m/z (Irel, %): 170.10 (100) [M – H]+, 171 (83), 143
(63), 128 (16), 115 (36), 63 (40), 51 (50).
2-Methyl-8-hydroxyquinoline (3l). bp 64–65°C
(0.2 mmHg). 1Н NMR spectrum (СDCl3), δ, ppm: 2.72
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

1618
KHUSNUTDINOV et al.
s (3H, CH3), 7.14 d (1H, С7H, J = 7.6 Hz), 7.27 d (1H,
С5H, J = 4.4 Hz), 7.29 d (1H, С3H, J = 8.4 Hz), 7.38 t
(1H, С6H, J = 7.6 Hz), 8.02 d (1H, С4H, J = 8 Hz). 13С
NMR spectrum, δС, ppm: 24.82 (СН3), 110.32 (C7),
117.37 (C5), 122.57 (C3), 126.59 (C6), 127.98 (C4a),
136.04 (C4), 138.65 (C8a), 151.80 (C8), 156.77 (C2).
Mass spectrum, m/z (Irel, %): 159 (100) [M – H]+, 160
(12), 131 (53), 130 (24), 89 (4), 77 (7).
Chem., 2002, vol. 80, p. 589. DOI: 10.1139/V02-062.
10. Kavita, De, Legros, J., Crousse, B., and Bonnet-Delpon, D.,
J. Org. Chem., 2009, vol. 74, p. 6260. DOI: 10.1021/
jo9012699.
11. Khusnutdinov, R.I., Bayguzina, A.R., Aminov, R.I., and
Dzhemilev, U.M., Russ. J. Org. Chem., 2012, vol. 48,
p. 690. DOI: 10.1134/S1070428012050107.
12. Claret, P.A. and Osborne, A.G., Org. Magn. Reson.,
1976, vol. 8, p. 147. DOI: 10.1002/mrc.1270080309.
13. Derdau, V., Atzrodt, J., Zimmermann, J., Kroll, C., and
Brckner, F., Chem. Eur. J., 2009, vol. 15, p. 10397.
DOI: 10.1002/chem. 200901107.
14. Sridharan, V., Avendano, C., and Menendez, J.C.,
Tetrahedron, 2007, vol. 63, p. 673. DOI: 10.1016/
j.tet.2006.11.002.
15. Chakrabarty, M.R. and Hanrahan, E.S., J. Mol. Spectr.,
1969, vol. 30, p. 348. DOI: 10.1016/0022-2852(69)
90270-7.
16. Osborne, A.G., Tetrahedron, 1983, vol. 39, p. 2831.
DOI: 10.1016/S0040-4020(01)82455-8.
17. Jaroszewska, J., Wawer, I., and Oszczapowicz, J., Org.
Magn. Reson., 1984, vol. 22, p. 323. DOI: 10.1002/
mrc.1270220510.
18. Matsubara, Y., Hirakawa, S., Yamaguchi, Y., and
Yoshida, Z., Angew. Chem. Int. Ed., 2011, vol. 50,
p. 7670. DOI: 10.1002/anie.201102076.
19. Lu, B., Li, C., and Zhang, L., J. Am. Chem. Soc., 2010,
vol. 132, p. 14070. DOI: 10.1021/ja1072614.
20. Ramesh, C., Kavala, V., Kuo, C.-W., and Yao, C.-F.,
Tetrahedron Lett., 2010, vol. 51, p. 5234. DOI: 10.1016/
j.tetlet.2010.07.063.
21. Choi, H.Y., Srisook, E., Jang, K.S., and Chi, D.Y.,
J. Org. Chem., 2005, vol. 70, p. 1222. DOI: 10.1021/
jo048297x.
REFERENCES
1. Kouznetsov, V.V., Mendez, L.Y.V., and Gomez, C.M.M.,
Curr. Org. Chem., 2005, vol. 9, p. 141. DOI:
10.2174/1385272053369196.
2. Khusnutdinov, R.I., Bayguzina, A.R., and Dzhemilev, U.M.,
J. Organomet. Chem., 2014, vol. 768, p. 75. DOI:
10.1016/j. jorganchem.2014.06.008.
3. Yamashkin, S.A. and Oreshkina, E.A., Chem.
Heterocycl. Compd., 2006, vol. 42, no. 6, p. 701. DOI:
10.1007/s10593-006-0150-y.
4. Majumbar, K.C., Debnath, P., De, N., and Roy, B.,
Curr. Org. Chem., 2011, vol. 15, no. 11, p. 1760. DOI:
10.2174/ 138527211795656633.
5. Tsuji, Y., Nishimura, H., Huh, K.T., and Watanabe, Y.J.,
J. Organomet. Chem., 1985, vol. 286, p. 44. DOI:
10.1016/0022-328X(85)80058-9.
6. Tsuji, Y., Huh, K.T., and Watanabe, Y.J., J. Org.
Chem., 1987, vol. 52, p. 1673. DOI: 10.1021/jo00385a006.
7. Khusnutdinov, R.I., Bayguzina, A.R., and Aminov, R.I.,
Russ. J. Gen. Chem., 2015, vol. 85, p. 2725. DOI:
10.1134/S1070363215120105.
8. Monrad, R.N. and Madsen, R., Org. Biomol. Chem.,
2011, vol. 9, p. 610. DOI: 10.1039/c0ob00676a.
22. Chen, M.-Y., Hsu, M.-A., Liu, C.-Y., and Chow, T.J.,
J. Chin. Chem. Soc., 2004, vol. 51, p. 735. DOI:
10.1002/jccs.200400112.
9. Boyd, D.R., Sharma, N.D., Modyanova, L.V., Carroll, J.G.,
Malone, J.F., Allen, C.C.R., Hamilton, J.T.G., Gib-
son, D.T., Parales, R.E., and Dalton, H., Canad. J.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016