Photocatalytic tandem reaction of primary alcohols with arylamines in the synthesis of amides and alkylquinolines in the presence of a heterogeneous Fe(CrO2)2–TiO2/X system under aerobic conditions

Article abstract of DOI:10.1007/s11172-019-2417-3

A heterogeneous system Fe(CrO₂)₂–TiO₂/X (where X is promoter NiO, CuO, ZnO, Cr₂O₃, Fe₂O₃, PrOCl, TbOCl, LaOCl, or EuOCl) was prepared. The photocatalytic activity of the system was tested in the tandem reaction of primary alcohols (BnOH, EtOH) with arylamines aimed at synthesizing benzamides and substituted 2-methylquinolines under aerobic conditions at room temperature.

Full text of DOI:10.1007/s11172-019-2417-3

68
Russian Chemical Bulletin, International Edition, Vol. 68, No. 1, pp. 68—73, January, 2019
Photocatalytic tandem reaction of primary alcohols with arylamines
in the synthesis of amides and alkylquinolines in the presence of
a heterogeneous Fe(CrO ) —TiO /X system under aerobic conditions
2
2
2
A. R. Makhmutov
Bashkir State University,
2 ul. Z. Validi, 450076 Ufa, Russian Federation.
Fax: +7 (347 84) 4 0455. E-mail: ainurmax@mail.ru
3
A heterogeneous system Fe(CrO ) —TiO /X (where X is promoter NiO, CuO, ZnO, Cr O ,
2
2
2
2
3
Fe O , PrOCl, TbOCl, LaOCl, or EuOCl) was prepared. The photocatalytic activity of the
2
3
system was tested in the tandem reaction of primary alcohols (BnOH, EtOH) with arylamines
aimed at synthesizing benzamides and substituted 2-methylquinolines under aerobic conditions
at room temperature.
Key words: benzamides, alkylquinolines, benzyl alcohol, ethanol, arylamines, photocatalysis,
iron chromite, titanium dioxide.
Photoactivation and photocatalysis provide new pos-
The photocatalytic activity of heterogeneous chromite
Fe(CrO ) in the oxidation of alcohols with Н О to the
sibilities for enhancing selectivity and efficiency of the
heterogeneous catalytic systems,1 since organic com-
pounds, in particular, nitrogen-containing organic sub-
stances, can be synthesized under milder conditions
2
2
2
2
—3
corresponding aldehydes followed by the condensation of
aldehydes with arylamines to alkyl-substituted quinolones
1
5
has recently been discovered. The use of chromite can
favor the development of the tandem synthesis of nitrogen-
containing organic compounds of diverse types, including
amides, by the reactions of alcohols with amines under
mild environmentally friendly conditions. Unlike the
nanocatalytic structures and ruthenium complexes, cata-
(
aqueous medium, atmospheric pressure, room tempera-
4
ture) than in the presence of traditional catalysts.
Nitrogen-containing functional groups, for example,
amide group and quinolone cycle, are components of many
synthetic and natural compounds applied in the pharma-
ceutical branch, oil-and-gas industry, agroindustrial
complex, and nanoelectronics.5
lytically active chromite Fe(CrO ) can be obtained from
2
2
,6
available and abundant reagents by the photochemical
Direct oxidative amidation from alcohols and amines
is an attractive method for amide synthesis, which is con-
sistent with the green chemistry concept.7 The use of
alcohols as reactants of the tandem synthesis is advanta-
geous due to their availability, low storage expenses, and
reaction of FeCl •6H O and K Cr O in an aqueous-
3
2
2
2
7
4
alcohol medium.
,8
In this work, we describe the photochemical synthesis
of the catalytic combined system Fe(CrO ) —TiO /Х
2
2
2
(Х is promoter NiO, CuO, ZnO, Cr O , Fe O , PrOCl,
2
3
2
3
9
the possibility to reduce the number of synthesis steps.
TbOCl, LaOCl, or EuOCl taken in an amount of 1.0 mol.%
The development of the nanocatalysis methods resulted
in the preparation of efficient heterogeneous catalytic
systems based on Pd (see Ref. 6) and Au (see Refs 10—13)
nanoparticles on special supports, for example, on graph-
with respect to TiO ). The results of testing the photo-
2
catalytic activity of Fe(CrO ) —TiO /Х in the tandem
2
2
2
reaction of primary alcohols (BnOH, EtOH) with aryl-
amines are also presented.
6
ene oxide (GO). These systems can perform the tandem
synthesis of aliphatic, aromatic, and cyclic (lactam) amides
of various classes directly from alcohols in the presence of
Results and Discussion
Н О or under aerobic conditions. At the same time, the
The photocatalytic effect of chromite Fe(CrO ) in the
2
2
2 2
synthesis of these nanostructural catalysts is fraught with
synthesis of alkylquinolines becomes fully apparent only
1
4
15
very high expenses. The ruthenium complexes are alter-
native efficient catalytic systems for the synthesis of amides
by the dehydrogenation of alcohols and hemiamines with
hydrogen evolution. However, these complexes must be
regenerated after the reaction completion.
in the presence of an aqueous solution of Н О . As a rule,
2
2
the work with media containing a strong oxidant requires
special security measures, which considerably compli-
cates the technology of synthesis and purification of reac-
tion products thus increasing the risk of emergency
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 0068—0073, January, 2019.
066-5285/19/6801-0068 © 2019 Springer Science+Business Media, Inc.
1

Synthesis of amides and alkylquinolines
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 1, January, 2019
69
conditions.16 A combination of chromite Fe(CrO ) with
The main features of the photocatalytic synthesis of
2
2
the known semiconductor photocatalyst of alcohol oxidation
amides and alkylquinolines under the action of the
Fe(CrO ) —TiO /Х system were studied on the model
by titanium dioxide17 into a single system Fe(CrO ) —TiO
2
2
2
2 2
2
makes it possible to avoid the application of such active
tandem reactions of BnOH and EtOH with aniline (1a).
The model of photocatalytic synthesis of benzanilide (2a)
and 2-methylquinoline (3a) under the action of the
oxidants as Н О , NaClO, and others. Oxidizing power of
2
2
air oxygen is sufficient to function efficiently as an oxidant
1
8
of the Fe(CrO ) —TiO photocatalytic system. A simi-
Fe(CrO ) —TiO /Х system is presented in Scheme 1.
2
2
2
2 2 2
lar combination of the copper(II) complexes with the Schiff
bases on TiO led to the synthesis of hybrid systems of the
The model process occurs in two different directions
depending on the alcohol nature. The tandem reaction
photooxidation—amidation occurs in the presence of
aromatic alcohol BnOH (route A) to form benzanilide (2a)
as the major product. The tandem reaction photooxid-
ation—cyclocondensation is observed for aliphatic alcohol
EtOH (route B), and the major product of the process is
2-methylquinoline (3a).
2
complex—TiO type, which are efficient photocatalysts of
2
IV
19
oxidation of the Cr compounds in methanol.
The combined Fe(CrO ) —TiO system was syn-
2
2
2
thesized by the photochemical precipitation of chro-
mite Fe(CrO2)2 from an aqueous-ethanol solution of
FeCl •6H O and K Cr O on the surface of a TiO sus-
3
2
2
2
7
2
pension under the irradiation with a Hg lamp at 25 С for
2
00 min. The average particle size of the Fe(CrO ) —TiO
Scheme 1
2
2
2
system determined by the laser diffraction method is
1
.8 m. The crystals of chromite Fe(CrO ) obtained in
2 2
the photochemical reaction in the absence of a TiO sus-
2
pension are larger: on the average 11.5 m.
The photocatalytic activity of TiO depends on the
2
presence of modifying additives (promoters), in particular,
the d- and f-metal compounds.2
0—23
The d-metal oxides
(
(
1
NiO, CuO, ZnO, Cr O , Fe O ) and f-metal oxychlorides
2 3 2 3
PrOCl, TbOCl, LaOCl, EuOCl) taken in an amount of
.0 mol.% with respect to TiO were used in this work as
2
promoters (X) of the Fe(CrO ) —TiO /Х system. The
2
2
2
2
4
procedure of catalyst preparation was described earlier.
i. 1 mol.% Fe(CrO ) —TiO /Х, oxidant, solvent, λ < 400 nm,
2
2
2
Samples of the Fe(CrO ) —TiO /Х system were used
2
2
2
25 C.
as photocatalysts of the tandem reaction for the synthesis
of amides from benzyl alcohol (BnOH) and of alkyl-
quinolines from ethanol (EtOH) with arylamines in the
presence of atmospheric air oxygen under irradiation with
a Hg lamp.
The effects of the oxidant and solvent and the duration
of the tandem process on the conversion of the initial
compound 1a and the yields of the reaction products 2a
and 3a are shown in Table 1.
Table 1. Influence of the nature of the oxidant and solvent and process time on the photocatalytic activity of the
a
Fe(CrO ) —TiO system in the model reactions
2
2
2
Oxidant
Solventb
τ/h
Route A
Route B
Conversion
Yield
Conversion
Yield
of arylamine 1a of benzamide 2a
of arylamine 1a of 2-methylquinoline 3a
O2(air)
—
2
DMSO
MeCN
16
16
16
16
16
16
24
24
16
16
11
14
15
19
15
16
17
17
13
25
86
57
14
17
18
13
11
16
17
13
22
18
92
73
H O
18
17
12
14
Dioxane
Toluene
11
15
10
19
H O
15
29
2
DMSO
27
23
d
H O
(H O)
>99
>99
>99
>99
2
2
2
d
NaClO
(H O)
2
a
Here and in Tables 2 and 3, the conversion of the initial compound and yields of the product are given in %.
b
c
Solvent content 1.5 mol; (Н О) is an aqueous solution of oxidants.
2
Bubbling with atmospheric air.
Weight content of the active substance is 10%.
d

7
0
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 1, January, 2019
Makhmutov
Oxygen of atmospheric air is inferior to active oxidants
2
absence of an efficient route of charge separation in the
indicated photocatalytic systems and low reduction poten-
tials of oxides that prevent their reduction to metals under
H O and NaClO in oxidation activity. However, the
2
elongation of the time of the model process under aerobic
conditions to 24 h allows one to increase the conversion
of compound 1a and yields of products 2a and 3a.
The influence of the solvents was observed for aqueous
solutions and DMSO. The effect of DMSO is most favor-
able for the synthesis of product 2a, i.e., it facilitates the
tandem reaction photooxidation—amidation (route A).
No influence of other solvents, acetonitrile, dioxane, and
toluene, on the conversion of compound 1a and the yields
of the products of the model reactions was recorded. The
parameters in the presence of these solvents were close to
those in the absence of solvent.
2
4
the photocatalytic conditions.
A specific feature of the photochemical behavior of the
TiO2 composites containing iron oxides as modifiers,
which were prepared by thermal sintering or iron nitrate
decomposition on the TiO surface, is the initiation of the
2
chain reaction
Fe3+ + e Fe2+; Fe2+ + h  Fe3+.
–
+
This reaction opposes an efficient charge separation
and substantially diminishes the photocatalytic activity of
2
3
TiO2. Nevertheless, some data indicate quite opposite,
favorable effect of doping TiO with iron ions in the case
The influence of the nature of the promoter (Х) of the
2
2
1,22
photocatalytic system Fe(CrO ) —TiO /Х on the conver-
of the photocatalytic processes.
The phenomenon is
2
2
2
sion of compound 1a and the yield of the products of the
explained by the ability of iron ions to capture and trans-
fer photogenerated electrons and holes. However, we did
model reactions under the action of O2(air) in a medium
of DMSO and H O for 24 h is presented in Table 2.
not observe any appreciable influence of Fe O as a pro-
2
2 3
The maximum conversion of compound 1a and high
moter in the studied Fe(CrO ) —TiO system on the
2
2
2
yields of products 2a and 3a are observed only for the NiO
model reaction (see Scheme 1).
and CuO promoters, i.e., for the Fe(CrO ) —TiO /NiO
Lanthanide oxychlorides were also tested as promoters
2
2
2
and Fe(CrO ) —TiO /CuO systems (see Table 2). This is
of the Fe(CrO ) —TiO system (see Table 2). The effi-
2
2
2
2 2 2
probably related to the reduction of modifying oxides NiO
ciency of the lanthanide promoters is lower than that of
the d-metal oxides and decreases in the following series:
PrOCl > TbOCl > LaOCl > EuOCl. For the first time,
the dependence of the photocatalytic activity of titanium
dioxide on the nature of the doped lanthanide ion was
0
0
and CuO to the corresponding metals Ni and Cu under
the photocatalytic conditions, which exerts a positive effect
on the tandem reaction as a whole. For example, it is
known that nickel as a cocatalyst (promoter, modifier) of
2
3
TiO enhances the oxidation rate of isopropyl alcohol with
observed in nitrite ion oxidation.
2
2
4
gaseous hydrogen evolution.
The influence of functional groups (R) of arylamines
(1b—f) on the efficiency of the photocatalytic tandem
reaction aimed at synthesizing the corresponding benz-
amides (2b—f) and 2-methylquinolines (3b—f) under the
The conversion of compound 1a and the yields of
target products 2a and 3a in the model reactions using
promoters ZnO, Cr O , and Fe O are comparable with
2
3
2
3
the parameters found for the initial system Fe(CrO ) —
action of O2(air) was studied for the Fe(CrO ) —TiO /CuO
2
2
2 2 2
TiO without a promoter. Probably, this is caused by the
photocatalytic system as an example (Scheme 2).
2
Table 2. Effect of the promoter (Х) on the photocatalytic activity of the Fe(CrO ) —TiO /Х system
2
2
2
in the model reactions under aerobic conditions
Promotera
Route A
Route B
Conversion
Yield
Conversion
Yield
of arylamine 1a of benzamide 2ab
of arylamine 1a of 2-methylquinoline 3a
c
Without
promoter
NiO
27
25
29
22
>99
>99
29
89
81
27
22
19
23
41
23
25
>99
>99
33
76
82
21
24
24
28
37
21
33
CuO
ZnO
Cr O
2
27
31
2
3
3
Fe O
25
27
LaOCl
PrOCl
EuOCl
TbOCl
28
35
42
49
27
29
29
42
a
The modifier content is 1.0 mol.% based on TiO2.
Solvent DMSO (1.5 mol).
b
c
Solvent Н О (1.5 mol).
2

Synthesis of amides and alkylquinolines
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 1, January, 2019
71
Table 3. Influence of the nature of arylamines on the photocatalytic activity of the Fe(CrO ) —TiO /CuO
2
2
2
a
system in the syntheses of benzamides and 2-methylquinolines
Arylamine Route A
Route B
Conversion
of arylamine 1a—f
Yield
Conversion
Yield
of benzamide 2а—fb
of arylamine 1a—f of 2-methylquinoline 3а—f
c
1
1
1
1
1
1
a
b
c
d
e
f
>99
>99
89
81
78
86
60
72
62
>99
>99
86
82
85
83
64
55
73
65
67
76
68
59
77
a
b
c
Atmospheric air oxygen as an oxidant.
Solvent DMSO (1.5 mol).
Solvent Н О (1.5 mol).
2
Scheme 2
with the formation of polyanilines and to photodestruc-
tion. The yields of reaction products 2c—f and 3c—f and
the conversion value of arylamines with the substituents
in the para-position 1c—f are close, indicating insignificant
contribution of processes of arylamine photodestruction
under UV irradiation with no photopolymerization. The
minimum photocatalytic effect of the Fe(CrO ) —TiO /
2
2
2
CuO system is observed for halosubstituted arylamines.
The mechanism of action of various forms of TiO2
during the photogenerated oxidation of alcohols with air
•
oxygen via photogeneration of active radical species ( ОН,
•
–
17
О , and others) has been described. It was also proved that
2
•
hydroxyl particles ( ОН) were selectively formed on the
R = o-Me (b), p-Me (c), p-Cl (d), p-Br (e), p-OH (f)
25
TiO in aqueous-alcohol systems. We found a similar
2
•
selective photogeneration of ОН particles in an aqueous-
i. 1 mol.% Fe(CrO ) —TiO /CuO, O2(air), λ < 400 nm, 25 C.
2
2
2
alcohol system for the oxidation of alcohols to aldehydes
4
Since arylamines 1a and 1b have no substituents in the
para-position relative to the amino group, they are com-
pletely converted in the photocatalytic processes (Table 3).
However, the yield of the target products 2a,b and 3a,b is
somewhat lower than the conversion value, because some
portion of arylamine is consumed to photo polymerization
under the action of chromite Fe(CrO ) . Thus, the initial
2
2
step of the photocatalytic synthesis of amides and alkylquin-
olines from primary alcohols BnOH and EtOH in the pres-
ence of the Fe(CrO ) —TiO /Х system under irradiation
2
2
2
with a Hg lamp starts, most probably, with the generation
•
of hydroxyl particles ОН (Schemes 3 and 4, respectively).
Scheme 3

72
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 1, January, 2019
Makhmutov
Scheme 4
Hydroxyl radicals are active oxidation species and
program complex based on Khromatek-Kristall 5000.1 and 5000.2
chromatographs (columns Agilent Technologies 19091F-413
HP-FFAP, 30 mЅ0.32 mm, 0.25 m; Analytical Science,
30 m0.32 mm, 0.5 m).
convert alcohols to aldehydes. Then azomethine (Az-I) is
formed from benzaldehyde in the presence of aniline (1a),
5
and the oxidation of Az-I leads to benzanilide (2a) (see
1H and 13C NMR spectra were recorded on the equipment
of the Center for Collective Use "Chemistry" of the Ufa Institute
of Chemistry (Russian Academy of Sciences): Bruker Avance III
Scheme 3). The photocatalytic oxidation of EtOH to acet-
aldehyde in the presence of aniline (1a) (see Scheme 4)
affords the Schiff base in two isomeric forms: aldimine
1
pulse spectrometers with the working frequencies 500.13 ( H)
1
3
(
Az-II) and enamine (Az-III). The reaction of the azomethine
and 125.47 ( C) MHz relative to the signal from Me Si as an
4
forms Az-II and Az-III under the action of the catalytic
internal standard.
system (chromite moiety) results in 1,2-dihydroquinaldine
Prior to experiments, the initial reagents, namely, benzyl
alcohol (BnOH, analytical pure grade, AO Reakhim), ethanol
4
(
3-Н). The final target product 2-methylquinoline (3a)
(
EtOH, reagent grade, AO EKOS-1), aniline (analytical pure
is formed due to the oxidation of compound 3-Н.
grade, AO Reakhim), dimethyl sulfoxide (DMSO, reagent grade,
To conclude, the photocatalytic activity of the com-
AO Reakhim), acetonitrile (CH CN, special pure grade, OOO
3
bined system Fe(CrO ) —TiO /Х (Х is promoter NiO, CuO,
2
2
2
NPK KRIOKhROM), dioxane (reagent grade, AO EKOS-1),
toluene (reagent grade, AO EKOS-1), and diethyl ether (anal-
ytical pure grade, AO Reakhim), were distilled according to
ZnO, Cr O , Fe O , PrOCl, TbOCl, LaOCl, or EuOCl)
2
3
2
3
was studied in the tandem reaction aimed at synthesizing
benzamides and substituted 2-methylquinolines. The
optimum conditions of the reaction were determined in-
cluding the promoter, oxidant, solvent, and process time.
The maximum efficiency with respect to the yield of the target
products under mold aerobic conditions was observed for
2
6
described procedures.
The reagents for the synthesis of the photocatalysts, namely,
FeCl •6H O (pure grade, OAO Brom), K Cr O (reagent grade,
3
2
2
2
7
ZAO Russkii Khrom), TiO (special pure grade, ZAO Prom-
2
khimperm), Fe(NO ) •9H O, Zn(NO ) •6H O, Ni(NO ) •
3
3
2
3 2
2
3 2
•
6H O (pure, AO LenReaktiv), Cu(NO ) •3H O,
2
3
2
2
the photocatalytic system Fe(CrO ) —TiO /CuO. The
2
2
2
Cr(NO ) •9H O (analytical pure grade, AO LenReaktiv), and
3
3
2
probable mechanism was proposed for the tandem photo-
catalytic synthesis of benzanilide and 2-methylquinoline.
LaCl •6H O, PrCl •6H O, EuCl •6H O, and TbCl •6H O
3
2
3
2
3
2
3
2
(
Alfa Aesar GmbH & Co KG, Reacton*, 99.9% REO) were used
as received.
The oxidants were an aqueous solution of H O (10 wt.%)
2
2
Experimental
prepared from a commercial 30% solution of hydrogen peroxide
special pure grade, OOO Lega) and an aqueous solution of
hypochlorite NaOCl (10 wt.%) prepared from chloride of lime
(
A GCMS-QP2010S Ultra GC-MS spectrometer (Shimadzu,
column Restek Rtx-5MS, 30 mЅ0.25 mm, 0.25 m) was used
for the identification of the reaction products. The quantitative
content of the reaction products was analyzed with an apparatus
2
7
(trade mark A, ZAO Vekton) as described previously.
Aerobic photocatalytic tandem synthesis of amides and alkyl-
quinolines (general procedure). The photocatalytic synthesis of

Synthesis of amides and alkylquinolines
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 1, January, 2019
73
amides and alkylquinolines from primary alcohols was carried
out in a Photo Catalytic Reactor Lelesil Innovative Systems
photocatalytic system with a 250-mL quartz reactor (photoreac-
tor of Stromeyer´s type with magnetic stir bar). The photoreac-
tor flask was loaded with a photocatalyst paste (5.0 g correspond-
ing to 1 mol.% with respect to alcohol), alcohol (BnOH or EtOH,
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3
a—d (see Ref. 28) are consistent with the literature data.
N-(2´-Methylphenyl)benzamide (2b). M.p. 145—146 С.
1
2
1
Н NMR (DMSO-d ), : 2.32 (s, 3 Н, С(2)Me); 7.09—7.80
6
1
13
(
m, 9 H, 2 Ph); 7.85 (br.s, 1 H, NH). С NMR (DMSO-d ), :
6
2
1
9.37 (Me), 125.53 (С(6´)), 125.81 (С(5´)), 126.76 (С(4´)), 127.27
1
(
1
С(2), C(6)), 128.09 (С(3), C(5)), 130.04 (С(3´)), 133.65 (С(2´)),
31.24 (С(4)), 134.56 (С(1)), 136.82 (С(1´)), 165.23 (С=O). MS
1
(
(
EI, 70 eV), m/z (Irel (%)): 212 (6), 211 [M]+ (42), 106 (12), 105
100), 77 (37).
3
1
N-(4´- Methylphenyl)benzamide (2c). M.p. 158—159 С.
1
1
Н NMR (DMSO-d ), : 2.35 (s, 3 Н, С(2)Me); 7.08—7.90
6
1
7. M. M. Gibert, in Photocatalytic Oxidation of Ethanol Using
13
(
m, 9 H, 2 Ph); 8.04 (br.s, 1 H, NH). С NMR (DMSO-d ), :
6
Macroporous Titania, Louisiana State University, Baton
2
0.77 (Me), 122.51 (С(2´), C(6´)), 128.57 (С(2), C(6)), 129.62
Rouge, 2008, p. 135.
(
(
(
С(3), C(5)), 130.38 (С(3´), C(5´)), 132.42 (С(4)), 135.16
С(4´)), 136.18 (С(1)), 137.26 (С(1´)), 165.11 (С=O). MS
EI, 70 eV), m/z (Irel (%)): 211 [M]+ (41), 106 (10), 105 (100),
1
8. A. R. Makhmutov, S. M. Usmanov, Bashkir. Khim. Zh.
[
Bashkir Chem. J.], 2018, 1, 18 (in Russian).
1
9. N. Yoshida, A. A. Tsaturyan, T. Akitsu, Y. Tsunoda, I. N.
7
7 (45), 51 (9).
Shcherbakov, Russ. Chem. Bull., 2017, 66, 2057.
0. Y.-S. Jung, K.-H. Kim, T.-Y. Jang, Y. Tak, S.-H. Baeck, Curr.
Appl. Phys., 2011, 11, 358.
N-(4´-Chlorophenyl)benzamide (2d). M.p. 154—156 С.
2
1
Н NMR (DMSO-d ), : 7.26—7.90 (m, 9 H, 2 Ph); 8.15 (br.s,
6
1
H, NH). 13С NMR (DMSO-d ), : 121.82 (С(2´), C(6´)),
6
2
1. W. Y. Choi, A. Termin, M. R. Hoffmann, J. Phys. Chem,
1
27.75 (С(2), C(6)), 128.16 (С(4´)), 128.91 (С(3), C(5)), 129.07
1994, 51, 13669.
(
С(3´), C(5´)), 131.19 (С(4)), 135.15 (С(1)), 138.41 (С(1´)),
2
2
2
2. M. I. Litter, Appl. Catal., B: Environmental, 1999, 23, 89.
3. A.-W. Xu, Y. Gao, H.-Q. Liu, J. Catal., 2002, 207, 151.
4. A. R. Makhmutov, S. M. Usmanov, Bashkir. Khim. Zh.
+
1
65.86 (С=O). MS (EI, 70 eV), m/z (Irel (%)): 231 [M] (20),
1
06 (8), 105 (100), 77 (58), 51 (22).
-Bromo-2-methylquinoline (3e). M.p. 102—104 С. Н NMR
CDCl ), : 2.76 (s, 3 Н, С(2)Me); 7.49, 7.64 (both d, 1 Н each,
1
6
[
Bashkir Chem. J.], 2018, 2, 70 (in Russian).
(
3
2
2
5. H. Zhang, W. Zhang, M. Zhao, P. Yang, Z. Zhu, Chem.
Commun., 2017, 53, 1518.
H(3), H(7), J = 7.6 Hz); 7.76 (s, 1 Н, Н(5)); 7.94 (d, 1 Н, H(4),
13
J = 7.6 Hz); 8.10 (d, 1 Н, H(8), J = 8.4 Hz). С NMR, : 28.57
Me), 129.18 (С(3)), 134.49 (С(4а)), 136.39 (С(5)), 139.81 (С(8)),
40.26 (С(7)), 140.72 (С(4)), 149.48 (С(6)), 155.36 (С(8а)),
58.65 (С(2)). MS (EI, 70 eV), m/z (I (%)): 223 (100), 222
6. A. Weissberger, E. S. Proskauer, J. A. Riddick, E. E. Toops,
Technics of Organic Chemistry, Vol. 7. Organic Solvents:
Physical Properties and Methods of Purification, Wiley, New
York, 1955.
(
1
1
rel
+
[
M] (17), 221 (97), 142 (40), 115 (52).
-Hydroxy-2-methylquinoline (3f). M.p. 214—218 С.
Н NMR (CDCl ), : 2.52 (s, 3 Н, С(2)Me); 7.03 (d, 1 Н, H(5),
2
7. Yu. V. Karyakin, I. I. Angelov, in Chistye khimicheskie
veshchestva [Pure Chemical Substances], Khimiya, Moscow,
6
1
3
1974, p. 285 (in Russian).
J = 2.6 Hz); 7.18, 7.72 (both d, 1 Н each, H(7), H(8), J = 8.3 Hz);
2
8. A. R. Makhmutov, Russ. J. Gen. Chem., 2018, 88, 892.
7
.21, 7.96 (both d, 1 Н each, H(3), H(4), J = 8.1 Hz); 9.83
13
(
s, 1 Н, OH). С NMR, : 24.80 (Me), 108.54 (С(5)),
21.36 (С(7)), 122.83 (С(3)), 127.08 (С(4a)), 129.97 (С(8)),
34.49 (С(4)), 142.54 (С(8a)), 155.69 (С(6)), 156.19 (С(2)). MS
EI, 70 eV), m/z (Irel (%)): 160 (11), 159 [M]+ (100), 131 (32),
30 (79), 103 (9).
1
1
Received July 16, 2018;
in revised form October 4, 2018;
accepted November 15, 2018
(
1