Synthesis and structure of 5,7-diisopropyl-2-(quinolin-2-yl)-1,3-tropolone derivatives

Article abstract of DOI:10.1007/s11172-016-1607-5

A synthetic procedure towards 4,6-diisopropyl-3-nitro-1,2-benzoquinone was elaborated. Based on this benzoquinone, a series of novel 5,7-diisopropyl-2-(quinolin-2-yl)-1,3-tropolones and 5,7diisopropyl-2-(quinolin-2-yl)-4-nitro-1,3-tropolones were derived. Molecular structure of 2-(4-chloro-8-methylquinolin-2-yl)-5,7-diisopropyl-1,3-tropolone was established by X-ray diffraction analysis. Energetic and structural characteristics of isomeric 5,7-diisopropyl-2-(quinolin-2yl)-1,3-tropolones and 5,7-diisopropyl-2-(quinolin-2-yl)-4-nitro-1,3-tropolones in the gas phase and in the polar solvent were calculated by quantum chemistry method (PBE0/6-311+G(d,p)).

Full text of DOI:10.1007/s11172-016-1607-5

Russian Chemical Bulletin, International Edition, Vol. 65, No. 10, pp. 2461—2468, October, 2016
2461
Synthesis and structure
of 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone derivatives
a,b
Nghia Bang Duong,c E. A. Gusakov, I. V. Dorogan, V. V. Tkachev,
b
b
d
Yu. A. Sayapin,
b
b
c
c
d
V. S. Gorkovets, V. N. Komissarov, Ngoc Toan Duong, Dang Duc Nguyen, G. V. Shilov,
d
a,b
S. M. Aldoshin, and V. I. Minkin
aSouthern Research Center of Russian Academy of Sciences,
1 ul. Chekhova, 344006 RostovꢀonꢀDon, Russian Federation.
Fax: +7 (863 2) 66 5677. Eꢀmail: sayapin@ipoc.sfedu.ru
4
b
Institute of Physical and Organic Chemistry, Southern Federal University,
1
94/2 prosp. Stachki, 344090 RostovꢀonꢀDon, Russian Federation.
Fax: +7 (863 2) 45 4700. Eꢀmail: minkin@ipoc.sfedu.ru
c
Thai Nguyen University of Sciences,
Tan Thinh Ward, Thai Nguyen City, Socialist Republic of Vietnam.
Fax: +84 (2803) 74 6965. Eꢀmail: duongbang2009@gmail.com
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
d
1
prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation.
Eꢀmail: vatka@icp.ac.ru
A synthetic procedure towards 4,6ꢀdiisopropylꢀ3ꢀnitroꢀ1,2ꢀbenzoquinone was elaborated. Based
on this benzoquinone, a series of novel 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolones and 5,7ꢀ
diisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ4ꢀnitroꢀ1,3ꢀtropolones were derived. Molecular structure of 2ꢀ(4ꢀ
chloroꢀ8ꢀmethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ1,3ꢀtropolone was established by Xꢀray diffracꢀ
tion analysis. Energetic and structural characteristics of isomeric 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀ
yl)ꢀ1,3ꢀtropolones and 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ4ꢀnitroꢀ1,3ꢀtropolones in the gas phase
and in the polar solvent were calculated by quantum chemistry method (PBE0/6ꢀ311+G(d,p)).
Key words: quinolines, 4,6ꢀdiisopropylꢀ3ꢀnitroꢀ1,2ꢀbenzoquinone, 1,3ꢀtropolones, intramoꢀ
lecular hydrogen bond, quantum chemistry calculations, Xꢀray diffraction analysis.
7
βꢀThujaplicin (hinokitiol, 2ꢀhydroxyꢀ4ꢀisopropylꢀ
cycloheptaꢀ2,4,6ꢀtrieneꢀ1ꢀone (1)) is of special interest
for medicinal chemistry. This compound was first found
by T. Nozoe in 1936 upon studying the essential oil of
Taiwan Hinoki (Taiwan cypress). Due to its antioxidant
properties, hinokitiol is widely used in cosmetics industry.
human gastric signet ring carcinoma KATO III, murine
8
melanoma B16ꢀF10 ), efficiently inhibits catechol
Oꢀmethyltransferase, matrix metalloproteinase, carboxꢀ
ypeptidase A, collagenase, and thermolysin, shows inꢀ
hibitory activity on the plant growth. Hinokitiol is a
platelet glycoprotein VI agonists and impaired convulxinꢀ
9
1
0
1
1
1
2
induced platelet aggregation. Hitokitiol inhibits growth
of Candida albicans and cells of human colon cancer
1
3
1
4
cell lines HCTꢀ116 and SWꢀ620. It also inhibits phosꢀ
phorylation of phospholipase C (PLC)γ2, protein kinase
C (PKC), mitogenꢀactivated protein kinases (MAPKs),
and Akt in collagenꢀactivated human platelets and sigꢀ
nificantly reduces intracellular calcium mobilization and
hydroxyl radical formation. Due to its ability to comꢀ
pletely inhibit polyphenol oxidase (PPO) and tyrosinase,
hinokitiol is widely applied in food industry as a preserꢀ
1
5
1
6—19
vative.
It has been demonstrated that hinokitiol has antimiꢀ
Recently, it has been demonstrated that the extracelꢀ
lularꢀsignalꢀregulated kinase (ERK) and p38 mitogenꢀacꢀ
tivated protein kinase (p38MAPK) pathways are inꢀ
volved in hinokitiolꢀinduced vascular endothelial growth
1
—4
crobial and antifungal activities,
pronounced insectiꢀ
cidal properties,5 exhibits cytotoxicity against human
,6
and murine tumor cell lines (human leukemia HLꢀ60,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2461—2468, October, 2016.
066ꢀ5285/16/6510ꢀ2461 © 2016 Springer Science+Business Media, Inc.
1

2462
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
Sayapin et al.
factor (VEGF) secretion in dental pulp cells. These
results indicate that hinokitiol promotes ERK and
p38MAPK activation and hinokitiolꢀinduced VEGF proꢀ
Scheme 1
duction thus increasing the angiogenic potential of denꢀ
tal pulp cells.2
0,21
Consequently, hinokitiol shows great
potential for treatment and prevention of dental disꢀ
eases.1
,22
Hinokitiol possesses potent neuroprotective
activity and can be used in treatment and prevention of
ischemia.23 A linalool—hinokitiol composition is highly
efficient against Pseudomonas aeruginosa, Moraxella
catarrhalis, Escherichia coli, Serratia marcescens, Staꢀ
phylococcus aureus, methicillinꢀresistant S. aureus
(
MRSA), Staphylococcus epidermidis, and Pityrosporum
2
4
25
ovale. We have recently demonstrated that the
2
1
ꢀ[benzo[2,3][1,4]oxazepino[7,6,5ꢀde]quinolineꢀ2ꢀyl]ꢀ
,3ꢀtropolone derivatives have in vitro cytotoxic effect
against MCFꢀ7 breast cancer cell lines.
Taking into account high biological activity of
tropones, development of the synthetic approaches to
access these compounds is an ongoing challenge. One of
the efficient approaches towards 2ꢀhetarylꢀsubstituted
droxyꢀ2,4ꢀcyclohexadieneꢀ1ꢀone derivatives (A) underꢀ
going further ring closure into norcaradiene derivatives
(
B) and rearrangement into dihydrotropolones (C). Oxiꢀ
dation of compound C with the excess of nitroꢀ1,2ꢀbenꢀ
zoquinone 4 leads to 4ꢀnitroꢀ1,3ꢀtropolones 7 in
30—50% yields. A competing reaction is a nitric acid
1
,3ꢀtropolones is the expansion of the orthoꢀquinone cycle
via the reactions of 1,2ꢀbenzoquinones with 2ꢀmethylꢀ
substituted nitrogen heterocycles.26 The desired funcꢀ
tional group can be introduced into the target
molecule abstraction and is accompanied by
a
1
6
,3ꢀsigmatropic hydrogen shift affording 1,3ꢀtropolones
in 8—24% yields. The synthesized 5,7ꢀdiisopropylꢀ2ꢀ
1
1
1
,3ꢀtropolone by varying the substituents in the starting
,2ꢀbenzoquinone. Since the synthetic procedures to give
,2ꢀbenzoquinones bearing the isopropyl groups are limꢀ
(
quinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolones (6) and 5,7ꢀdiisopropylꢀ
ꢀ(quinolinꢀ2ꢀyl)ꢀ4ꢀnitroꢀ1,3ꢀtropolones (7) are sumꢀ
marized in Table 1. The use of stoichiometric amounts of
and 5 in the reaction lowered the yields of tropolones 6
and 7.
2
ited, we elaborated a procedure to access 4,6ꢀdiisopropylꢀ
ꢀnitroꢀ1,2ꢀbenzoquinone. The synthesized derivatives
3
4
were used to derive a series of tropolones with promising
biological activity.
Structures of the synthesized compounds 6 and 7
1
Results and Discussion
were confirmed by H NMR and IR spectroscopy and
1
mass spectrometry. In H NMR spectra of these comꢀ
Refluxing pyrocatechol (2) in isopropyl alcohol in the
presence of sulfuric acid with simultaneous distillation of
the solvent27 produces 3,5ꢀdiidsopropylpyrocatechol (3)
pounds, the narrow singlets at δH 18—19 are attributed to
the hydroxy group protons involved in a strong hydrogen
bond with the quinolineꢀring nitrogen closing a sixꢀmemꢀ
bered chelate cycle. Protons of the tropolone cycle resoꢀ
nate in the δH 6.7—7.0 range.
Crystal structure of 2ꢀ(4ꢀchloroꢀ8ꢀmethylquinolinꢀ
2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ1,3ꢀtropolone (6g) was established
by single crystal Xꢀray diffraction analysis. Two molꢀ
ecules showing no differences in their structures are loꢀ
calized in the independent part of the unit cell; however,
it occurred impossible to apply a model with higher
pointꢀgroup symmetry. Therefore, only one independent
molecule of 6g is shown in Fig. 1. Complete crystalloꢀ
graphic data for 6g were deposited with the Cambridge
Crystallographic Data Centre (CCDC 1457753) and
can be obtained free of charge via www.ccdc.cam.ac.uk/
data_request/cif.
(
Scheme 1). Yield and purity of product 3 depend directly
on the amount of isopropyl alcohol distilled off. The
complete removal of propanꢀ2ꢀol leads to resinification,
but removal of the insufficient amount of alcohol impedes
the product crystallization. We found that the removal of
5
0—60% of the total alcohol volume is optimal and proꢀ
duces stable yield of the target pyrocatechol of 35—40%.
Oxidation of pyrocatechol 3 with diluted nitric acid
gives 4,6ꢀdiisopropylꢀ3ꢀnitroꢀ1,2ꢀbenzoquinone (4) in
low yield of 24% (see Scheme 1). Acetic acidꢀmediated
reaction of 1,2ꢀbenzoquinone 4 with 2ꢀmethylquinolines
5
produces 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀ
tropolones (6) and 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ
4
ꢀnitroꢀ1,3ꢀtropolones (7) (Scheme 2).
A mechanism of formation of 6 and 7 is given in
In the molecules, the intramolecular Hꢀbond with
the N(1)...H(2) distance of 1.57(2) Å (1.65(2) Å) (here
and hereafter, the parameters for the second molecule are
given in parenthesis), N(1)...O(2) 2.462(2) Å (2.461(2) Å)
Scheme 2. The process is started by aldol condensation
of 2ꢀmethylquinoline 5 with 4,6ꢀdiisopropylꢀ3ꢀnitroꢀ1,2ꢀ
benzoquinone (4) to give 6ꢀ(quinolinꢀ2ꢀylmethyl)ꢀ6ꢀhyꢀ

5,7ꢀDiisopropylꢀ2ꢀquinolylꢀ1,3ꢀtropolone derivatives Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
2463
Scheme 2
1
2
3
4
5
R = H, Cl; R = H, NO ; R = R = R = H, Me
2
Cl()
and the N—H—O angle of 155(2)° (147(2)°) is realized.
These values are close to the analogous parameters (1.52(2),
C(10)
C(11)
C(12)
O(1)
Table 1. Derivatives of 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀ
tropolones 6 and 7
C(9)
C(21)
C(13)
C(14)
C(19)
C(1)
C(16)
C(8)
Comꢀ
pound
R1
R2
R3
R4
R5
Y*
(%)
δOH
C(20)
N(1)
C(2) C(7)
C(15)
C(17)
C(6)
6
а
Cl
Cl
Cl
H
Cl
Cl
Cl
Cl
Cl
Cl
H
H
NO2
H
H
H
H
H
H
NO2
H
H
H
H
H
Me
Me
H
H
H
F
H
Me
Me
H
H
H
F
H
H
H
Me
H
H
H
H
H
H
Me
H
Me
Me
Me
H
H
H
Me
Me
Me
Me
H
13 19.53
10 18.19
16 19.68
H(2)
C(5)
C(4)
6b
C(3)
C(23)
6
c
O(2)
6
d
8
8
19.50
19.08
C(18)
6
e
6
f
10 18.20
24 19.53
39 19.06
35 19.34
40 18.88
29 18.90
51 19.07
38 19.46
50 19.02
6g
C(22)
7
a
7b
Fig. 1. Molecular structure of 5,7ꢀdiisopropylꢀ2ꢀ(4ꢀchloroꢀ8ꢀ
methylquinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone (6g) (the structure of only one
independent molecule is shown).
7
c
7
d
7
e
Cl
Cl
Cl
H
H
H
H
H
Me
7
f
7g
2
.457(1) Å and 157(2)°) found earlier28 for the related
compound differing from 6g by the presence of the tertꢀ
*
Y is the product yield.

2464
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
Sayapin et al.
Table 2. Selected bond lengths (d) and bond angles (ω) for compound 6g
Bond
d/Å
Bond
d/Å
Angle
ω/deg
O(1)—C(1)
O(2)—C(3)
O(2)—H(2)
N(1)—C(8)
C(1)—C(2)
C(1)—C(7)
C(2)—C(3)
1.239(4)
1.334(4)
0.8518
1.349(4)
1.470(5)
1.486(5)
1.405(5)
C(2)—C(8)
C(3)—C(4)
C(4)—C(5)
C(5)—C(6)
C(6)—C(7)
C(8)—C(9)
1.462(5)
1.454(5)
1.345(5)
1.452(5)
1.344(5)
1.433(5)
C(3)—O(2)—H(2)
O(1)—C(1)—C(2)
C(3)—C(2)—C(1)
C(3)—C(2)—C(8)
O(2)—C(3)—C(2)
N(1)—C(8)—C(2)
96.8
121.2(3)
122.0(3)
120.4(3)
121.2(3)
117.4(3)
butyl groups at the C(5) and C(7) atoms of the tropolone
cycle instead of isopropyl moieties. Overlaying the atoms
of the tropolone fragments of these two compounds reꢀ
veals the similarity of their structures. Note that the hyꢀ
drogen atoms at C(18) and C(19) of 6g are "replacements"
of the methyl groups of the tertꢀbutyl analog, which
in the latter are either directed from the tropolone
cycle (C(18)Me) or spatially proximal to the cycle
The tropolone cycle retains a boat conformation with
the C(2), C(3), C(5), and C(6) atoms being coplanar as
2
8
typical of earlier studied compounds.
It is of note that bonding of the hydrogen atom to
oxygen in the closely related structures is much seldom
event than bonding to nitrogen as in analogous 2ꢀhetarylꢀ
2
6,29
1,3ꢀtropolones.
To estimate the relative thermodynamic stabilities of
(
C(19)Me).
the OH and NH tautomers 6g and 7g, we calculated their
1
.429
1.359
.428
1.420
1.362
1.413
1
1.424
1.421
1
.229
1.226
1.469
1
.331
1
.347
1.495
1.491
1.362
1.354
1.439
1.466
1.472
1.350
1.079
1
.346
1
.439
1.486
1.401
1.439
1
.451
1.458
1.439
1
.032
1
.445
1.320
1.268
1.439
1.353
Cl
N
O
C
6g(NH)
6g(OH)
H
1
.428
1.361
1.420
1.354
1
.364
1.413
1.426
.347
1.421
1.421
1
.226
1.224
1
1.495
1.490
1.363
1.469
1.441
1.466
.434
1.470
1.469
.397
.448
1.353
1.060
1.345
1.349
1.439
1
1.431
1
1
.506
1
1
.445
1.055
1.259
1.310
1.348
7g(NH)
7g(OH)
Fig. 2. Structural parameters for tautomers 6g and 7g calculated at the PBE0/6ꢀ311+G(d,p) level of theory. Bond lengths are given in Å.

5,7ꢀDiisopropylꢀ2ꢀquinolylꢀ1,3ꢀtropolone derivatives Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
2465
Table 3. Zero point corrected total energies (Etot+ZPE/a.u.) and
relative energies (ΔE/kcal mol–1) of isomers of compounds 6g and
SiMe (internal standard). IR spectra were recorded on a Varian
3100FTꢀIR Excalibur Series instrument in attenuated total reflecꢀ
4
7
g computed at the PBE0/6ꢀ311+G(d,p) level of theory in the gas
tion mode. Electron impact (70 eV) mass spectrometry was perꢀ
formed with a Shimadzu GCMSꢀQP2010SE instrument using a
direct inlet. For column chromatography, Al O (Brockmann acꢀ
phase and in the DMSO solution
2
3
tivity grade II—III) was used. Melting points were measured in glass
capillaries using a PTP apparatus and are given uncorrected. IR and
NMR spectra were recorded using facilities of the Center of Collecꢀ
tive Use of Southern State University "Molecular Spectroscopy".
3,5ꢀDiisopropylpyrocatechol (3). A solution of pyrocatechol
(11 g, 0.1 mol) and concentrated H SO (5 mL) in isopropyl
alcohol (100 mL) was refluxed with a Liebig condenser with simulꢀ
taneous distillation of the solvent. After 55 mL of isopropyl alcohol
were distilled off, the reaction mixture was cooled and diluted with
cold water (200 mL). The precipitate was collected by filtration and
recrystallized from petroleum ether (b.p. 40—70 °C). Yield 35%.
Compoꢀ
und
Etot+ZPE(gas) ΔEgas
Etot+ZPE(sol)
ΔEsol
6g (NH)
6g (OH)
7g (NH)
7g (OH)
–1554.747777
0
–1554.759095
0
–0.3
0
–1554.749016 –0.8 –1554.759563
–1759.092692
–1759.09178
0
–1759.108953
2
4
0.6 –1759.106727
1.4
structural and energetic characteristics both in the gas
phase and DMSO solution at the PBE0/6ꢀ311+G(d,p)
level of theory (Fig. 2, Table 3).
Colorless crystals, m.p. 67—69 °C (from petroleum ether (b.p.
1
4
0—70 °C)). H NMR (CDCl ), δ: 1.20—1.27 (m, 12 H, Me);
3
It has been previously found26,29 that enhancement of
acceptor properties of the tropolone fragment leads to
the shift of equilibrium towards the NH isomer, while the
enhancement of the acceptor properties of the heterocyꢀ
clic moiety stabilizes the OH tautomer. The estimates of
the thermodynamic stabilities of tautomers 6g and 7g
2.79 (sept, 1 H, CH, J = 6.9 Hz); 3.18 (sept, 1 H, CH, J = 6.9 Hz);
4.51 (br.s, 2 H, OH); 6.60 (d, 1 H, Harom, J = 2.1 Hz), 6.64 (d, 1 H,
Harom, J = 2.1 Hz). Found (%): C, 74.00; H, 9.12. C12H18O2.
Calculated (%): C, 74.19; H, 9.34.
4
,6ꢀDiisopropylꢀ3ꢀnitroꢀ1,2ꢀbenzoquinone (4). To a solution
of pyrocatechol derivative 3 (10 g, 0.05 mol) in petroleum ether
b.p. 40—70 °C, 100 mL), 57% HNO (15—20 mL) was added and
(
3
(
Table 3) are in complete agreement with this concept.
the mixture was stirred at room temperature 30—60 min.
Nitroquinone is insoluble in petroleum ether and formed an oily
layer on a phase interface. Dilution of the mixture with water
(100 mL) led to precipitation of the oil. After decantation of the
upper layers, the oil was washed with water, and the aqueous layer
was decanted (Note. It is preferable to decant aqueous layer comꢀ
pletely). The oil was dissolved in isopropyl alcohol and the volatiles
were removed as much as possible. Upon cooling, the red crystals of
The acceptor substituent (the chlorine atom) at the quinoꢀ
line fragment of 6g stabilizes the OH form of the comꢀ
pound, which occurs more stable than the NH isomer in
both the gas phase (ΔE ) and polar solvent (ΔE ) by 0.8
gas
sol
–
1
and 0.3 kcal mol , respectively. On the contrary, introꢀ
duction of the nitro group into the tropolone fragment
(
compound 7g) decreases the energy of the NH form in
i
–1
4
1
1
precipitated, m.p. 125—127 °C (Pr OH). Yield 24%. IR, ν/cm :
such way that totally eliminates the effect of the acceptor
substituent at the quinoline moiety. As a result, the NH
isomer becomes more stable than the OH form in the gas
691, 1671, 1655, 1639, 1577, 1530, 1465, 1387, 1368, 1283,
247, 1184, 1103, 1037, 1011, 962, 908, 821, 805. 1H NMR
(
CDCl ), δ: 1.17 (s, 3 H, Me); 1.19 (s, 3 H, Me); 1.24 (s, 3 H, Me);
3
–
1
phase and in the polar solvent by 0.6 and 1.4 kcal mol
,
1.27 (s, 3 H, Me); 2.92 (sept, 1 H, CH, J = 6.9 Hz); 3.04 (sept, 1 H,
respectively. Thus, tautometic equilibria between NH and
OH forms of the tropolone derivatives can be easily afꢀ
fected by varying the electronic properties of the substituꢀ
ents at the tropolone and heterocyclic fragments.
CH, J = 6.9 Hz); 6.78 (d, 1 H, Harom, J = 1.2 Hz). Found (%):
C, 60.60; H, 6.25; N, 5.72. C H NO . Calculated (%): C, 60.75;
12
15
4
H, 6.37; N, 5.90.
Synthesis of 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolones
6a—g) and 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ4ꢀnitroꢀ1,3ꢀ
(
In summary, a series of new 5,7ꢀdiisopropylꢀ2ꢀ
tropolones (7a—g) (general procedure).
A solution of
(
2
quinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolones and 5,7ꢀdiisopropylꢀ
ꢀ(quinolinꢀ2ꢀyl)ꢀ4ꢀnitroꢀ1,3ꢀtropolones were first deꢀ
4
,6ꢀdiisopropylꢀ3ꢀnitroꢀ1,2ꢀbenzoquinone (4) (10 mL) and comꢀ
pound 5a—g (5 mmol) in glacial acetic acid (10 mL) was refluxed
for 3—5 h. After cooling, the reaction mixture was diluted with
water and extracted with dichloromethane. The combined organic
layers were dried with anhydrous sodium sulfate and the solvent was
removed in vacuo. The residue was subjected to column chromaꢀ
tography (alumina, elution with hexane—chloroform, 1 : 1) collectꢀ
ing the two first yellow fractions. The first fraction is compound
rived from 4,6ꢀdiisopropylꢀ3ꢀnitroꢀ1,2ꢀbenzoquinone.
Relative thermodynamic stabilities of OH and NH tauꢀ
tomers of 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀ
tropolones and 5,7ꢀdiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ4ꢀ
nitroꢀ1,3ꢀtropolones were estimated. Structure of
2
1
ꢀ(4ꢀchloroꢀ8ꢀmethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ
,3ꢀtropolone was established by Xꢀray diffraction analyꢀ
6
a—g, the second fraction is compound 7a—g. After removal of the
solvent in vacuo, the residues were recrystallized from propaneꢀ2ꢀol.
ꢀ(4ꢀChloroꢀ6,8ꢀdimethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ1,3ꢀ
tropolone (6a). Yield 13%. Yellow crystals, m.p. 140—142 °C
sis. It was revealed that in the crystal this compound
exists as the OH tautomer.
2
i
–1
(
Pr OH). IR, ν/cm : 3115, 1640, 1617, 1587, 1560, 1490, 1458,
Experimental
1408, 1352, 1300, 1277, 1223, 1192, 1158, 1096, 1069, 1039, 1022,
1
9
61, 943, 923, 882, 852, 825. H NMR (CDCl ), δ: 1.21
3
1H NMR spectra were recorded with a Varian Unityꢀ300 specꢀ
trometer. The chemical shifts are given in the δ scale relative to
(s, 12 H, Me); 2.51 (s, 3 H, Me); 2.64 (sept, 1 H, CH, J = 6.9 Hz);
.69 (s, 3 H, Me); 3.47 (sept, 1 H, CH, J = 6.9 Hz); 6.49 (d, 1 H,
2

2466
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
Sayapin et al.
Htrop, J = 1.2 Hz); 6.63 (d, 1 H, Htrop, J = 1.2 Hz); 7.44 (s, 1 H,
Harom); 7.79 (s, 1 H, Harom); 8.35 (s, 1 H, H ); 19.53 (br.s, 1 H,
OH). MS (EI, 70 eV), m/z (Irel (%)): 395 [M] (5), 369 (23), 368
7.91 (d, 1 H, Harom, J = 8.4 Hz); 8.32 (s, 1 H, H
); 19.68 (br.s,
arom
+
1 H, OH). MS (EI, 70 eV), m/z (Irel (%)): 395 [M] (4), 369 (24),
368 (24), 367 (67), 354 (35), 353 (25), 352 (100), 338 (13), 324 (13),
310 (10), 232 (4), 204 (4), 140 (4), 127 (6), 91 (6), 77 (6), 69 (8), 55
(10). Found (%): C, 72.74; H, 6.52; N, 3.46. C H ClNO . Calꢀ
arom
+
(
(
22), 367 (67), 366 (18), 355 (8), 354 (34), 353 (25), 352 (100), 338
13), 332 (8), 324 (13), 310 (10), 91 (5), 77 (5). Found (%):
2
4
26
2
C, 72.68; H, 6.56; N, 3.40. C H ClNO . Calculated (%): C, 72.81;
culated (%): C, 72.81; H, 6.62; N, 3.54.
24
26
2
H, 6.62; N, 3.54.
ꢀ(4ꢀChloroꢀ6,8ꢀdimethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ4ꢀ
nitroꢀ1,3ꢀtropolone (7a). Yield 39%. Yellow crystals, m.p. 208—
2ꢀ(4ꢀChloroꢀ7,8ꢀdimethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ4ꢀ
2
nitroꢀ1,3ꢀtropolone (7c). Yield 40%. Yellow crystals, m.p. 193—
i
–1
195 °C (Pr OH). IR, ν/cm : 3120, 1608, 1567, 1540, 1499, 1461,
i
–1
2
1
8
10 °C (Pr OH). IR, ν/cm : 3109, 1612, 1589, 1533, 1461, 1441,
1430, 1410, 1392, 1367, 1287, 1249, 1179, 1108, 1087, 1055, 1032,
1
405, 1392, 1366, 1283, 1234, 1097, 1033, 985, 929, 889, 864,
987, 946, 892, 873, 863, 851, 834, 813. H NMR (CDCl ), δ:
3
1
46, 828. H NMR (CDCl ), δ: 1.20 (s, 12 H, Me); 2.52 (s, 3 H,
1.21—1.24 (m, 12 H, Me); 2.56 (s, 3 H, Me); 2.64 (s, 3 H, Me);
2.73 (sept, 1 H, CH, J = 6.9 Hz); 3.45 (sept, 1 H, CH, J = 6.9 Hz);
6.37 (s, 1 H, Htrop); 7.46 (d, 1 H, Harom, J = 8.5 Hz); 7.94 (d, 1 H,
3
Me); 2.70 (s, 3 H, Me); 2.71 (sept, 1 H, CH, J = 6.9 Hz); 3.42
sept, 1 H, CH, J = 6.9 Hz); 6.36 (s, 1 H, Htrop); 7.48 (s, 1 H,
Harom); 7.80 (s, 1 H, Harom); 8.43 (s, 1 H, H ); 19.06 (br.s, 1 H,
(
Harom, J = 8.5 Hz); 8.41 (s, 1 H, H
); 18.88 (br.s, 1 H, OH).
arom
arom
+
+
OH). MS (EI, 70 eV), m/z (Irel (%)): 440 [M] (14), 414 (23), 413
22), 412 (67), 411 (18), 397 (27), 396 (21), 395 (27), 394 (49),
81 (12), 380 (13), 379 (34), 378 (22), 377 (42), 365 (19), 364
15), 352 (27), 351 (40), 350 (35), 337 (35), 336 (33), 323 (25),
32 (15), 168 (20), 97 (44), 85 (38), 83 (51), 81 (35), 71 (62), 69
65), 57 (100), 55 (82). Found (%): C, 65.22; H, 5.64; N, 6.24.
C H ClN O . Calculated (%): C, 65.38; H, 5.71; N, 6.35.
MS (EI, 70 eV), m/z (Irel (%)): 440 [M] (21), 414 (36), 412 (100),
411 (30), 394 (80), 379 (52), 377 (64), 365 (31), 351 (58),
350 (56), 337 (54), 336 (51), 323 (38), 308 (20), 266 (11),
232 (24), 204 (23), 190 (22), 168 (21), 154 (22), 127 (27), 105
(26), 97 (18), 85 (17), 83 (21), 77 (36), 69 (32), 57 (39), 55 (41).
Found (%): C, 65.16; H, 5.58; N, 6.20. C H ClN O . Calcuꢀ
(
3
(
2
(
2
4
25
2
4
lated (%): C, 65.38; H, 5.71; N, 6.35.
5,7ꢀDiisopropylꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone (6d). Yield
2
4
25
2
4
2
ꢀ(4ꢀChloroꢀ6,8ꢀdimethylꢀ5ꢀnitroquinolinꢀ2ꢀyl)ꢀ5,7ꢀ
i
1
diisopropylꢀ1,3ꢀtropolone (6b). Yield 10%. Yellow crystals, m.p.
8%. Yellow crystals, m.p. 120—122 °C (Pr OH). H NMR (CDCl ),
3
i
–1
1
1
1
1
73—175 °C (Pr OH). IR, ν/cm : 3111, 1641, 1600, 1575, 1535,
δ: 1.21—1.27 (m, 12 H, Me); 2.67 (sept, 1 H, CH, J = 6.9 Hz); 3.48
(sept, 1 H, CH, J = 6.9 Hz); 6.47 (d, 1 H, Htrop, J = 1.2 Hz); 6.61
(d, 1 H, Htrop, J = 1.2 Hz); 7.48—7.51 (m, 1 H, Harom); 7.68—7.69
(m, 1 H, Harom); 7.75—7.76 (m, 1 H, Harom); 7.81—7.84 (m, 1 H,
Harom); 8.12—8.14 (m, 1 H, Harom); 8.29 (m, 1 H, Harom); 19.50
(br.s, 1 H, OH). Found (%): C, 79.08; H, 6.72; N, 4.08.
C H NO . Calculated (%): C, 79.25; H, 6.95; N, 4.20.
488, 1461, 1410, 1374, 1346, 1296, 1253, 1233, 1193, 1133, 1101,
071, 1030, 1014, 992, 948, 923, 873, 838. H NMR (CDCl ), δ:
.21—1.26 (m, 12 H, Me); 2.44 (s, 3 H, Me); 2.72 (sept, 1 H, CH,
1
3
J = 6.9 Hz); 2.73 (s, 3 H, Me); 3.47 (sept, 1 H, CH, J = 6.9 Hz);
6
7
.60 (d, 1 H, Htrop, J = 1.5 Hz); 6.67 (d, 1 H, Htrop, J = 1.5 Hz);
.51 (s, 1 H, Harom); 8.35 (s, 1 H, Harom); 18.19 (br.s, 1 H, OH).
22
23
2
+
MS (EI, 70 eV), m/z (Irel (%)): 440 [M] (11), 415 (8), 414 (34),
5,7ꢀDiisopropylꢀ4ꢀnitroꢀ2ꢀ(quinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone (7d).
i
–1
413 (26), 412 (96), 400 (8), 399 (35), 398 (25), 397 (100), 383 (10),
378 (5), 353 (10), 351 (29), 323 (5), 308 (9), 288 (3), 272 (3),
231 (3), 140 (5), 139 (5), 115 (5), 91 (8), 77 (9), 55 (5). Found (%):
Yield 29%. Yellow crystals, m.p. 151—153 °C (Pr OH). IR, ν/cm :
3131, 1627, 1606, 1591, 1530, 1501, 1481, 1458, 1433, 1389, 1377,
1359, 1301, 1280, 1238, 1221, 1151, 1132, 1102, 1079, 1051, 1033,
1
C, 65.14; H, 5.56; N, 6.28. C24H25ClN O . Calculated (%):
998, 984, 962, 934, 906, 879, 868, 839, 803. H NMR (CDCl ),
2
4
3
C, 65.38; H, 5.71; N, 6.35.
ꢀ(4ꢀChloroꢀ6,8ꢀdimethylꢀ5ꢀnitroquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisoꢀ
propylꢀ4ꢀnitroꢀ1,3ꢀtropolone (7b). Yield 35%. Yellow crystals,
δ: 1.18—1.22 (m, 12 H, Me); 2.71 (s, 3 H, Me); 2.71 (sept, 1 H, CH,
J = 6.9 Hz); 3.42 (sept, 1 H, CH, J = 6.9 Hz); 6.33 (s, 1 H, Htrop);
7.51—7.57 (m, 1 H, Harom); 7.71—7.80 (m, 3 H, Harom); 8.14—
8.17 (m, 1 H, Harom); 8.22—8.26 (m, 1 H, Harom); 18.90 (br.s, 1 H,
2
i
–1
m.p. 238—240 °C (Pr OH). IR, ν/cm : 3105, 1637, 1617, 1582,
+
1
1
1
2
6
1
4
3
3
2
1
536, 1463, 1437, 1413, 1394, 1369, 1335, 1287, 1261, 1198, 1167,
OH). MS (EI, 70 eV), m/z (Irel (%)): 378 [M] (14), 350 (100),
1
106, 1033, 985, 932, 895, 879, 848, 799. H NMR (CDCl ), δ:
332 (76), 317 (42), 315 (52), 302 (29), 288 (64), 274 (58),
273 (52), 261 (32), 246 (25), 217 (29), 170 (20), 140 (47), 128
(92), 115 (37), 105 (18), 91 (32), 83 (15), 77 (44), 69 (20), 57 (25),
55 (35). Found (%): C, 69.62; H, 5.74; N, 7.34. C H N O .
3
.22—1.25 (m, 12 H, Me); 2.45 (s, 3 H, Me); 2.74 (s, 3 H, Me);
.78 (sept, 1 H, CH, J = 6.9 Hz); 3.42 (sept, 1 H, CH, J = 6.9 Hz);
.47 (s, 1 H, Htrop); 7.57 (s, 1 H, Harom); 8.41 (s, 1 H, Harom);
22 22
2
4
+
9.34 (br.s, 1 H, OH). MS (EI, 70 eV), m/z (Irel (%)): 485 [M] (8),
Calculated (%): C, 69.83; H, 5.86; N, 7.40.
59 (16), 457 (46), 439 (18), 423 (33), 422 (100), 409 (22), 403 (22),
96 (20), 395 (16), 378 (16), 377 (11), 365 (10), 364 (12), 352 (8),
50 (14), 335 (16), 322 (12), 300 (12), 299 (8), 256 (7), 242 (8),
41 (8), 231 (8), 204 (9), 202 (9), 190 (6), 166 (11), 127 (13),
15 (12), 105 (15), 91 (25), 77 (23), 65 (10), 55 (11). Found (%):
2ꢀ(4ꢀChloroquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ1,3ꢀtropolone (6e).
1
Yield 8%. Yellow oil. H NMR (CDCl ), δ: 1.22 (m, 12 H, Me);
3
2.69 (sept, 1 H, CH, J = 6.9 Hz); 3.47 (sept, 1 H, CH, J = 6.9 Hz);
6.52 (d, 1 H, Htrop, J = 1.2 Hz); 6.61 (d, 1 H, Htrop, J = 1.2 Hz);
7.55—7.60 (m, 1 H, Harom); 7.70—7.75 (m, 1 H, Harom); 7.85—
7.87 (m, 1 H, Harom); 8.12—8.15 (m, 1 H, Harom); 8.30 (s, 1 H,
Harom); 19.08 (br.s, 1 H, OH). Found (%): C, 71.68; H, 5.88; N, 3.68.
C H ClNO . Calculated (%): C, 71.83; H, 6.03; N, 3.81.
C, 59.24; H, 4.78; N, 8.44. C H ClN O . Calculated (%):
2
4
24
3
6
C, 59.32; H, 4.98; N, 8.65.
ꢀ(4ꢀChloroꢀ7,8ꢀdimethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ1,3ꢀ
tropolone (6c). Yield 16%. Yellow crystals, m.p. 129—131 °C
2
22
22
2
2ꢀ(4ꢀChloroquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ4ꢀnitroꢀ1,3ꢀ
tropolone (7e). Yield 51%. Yellow crystals, m.p. 148—150 °C
i
–1
(
Pr OH). IR, ν/cm : 3124, 1638, 1593, 1551, 1505, 1463, 1428,
i
1
1
8
384, 1350, 1310, 1280, 1233, 1194, 1177, 1087, 1039, 1018, 950,
(Pr OH). H NMR (CDCl ), δ: 1.21—1.24 (m, 12 H, Me); 2.74
3
1
79, 865, 832, 811. H NMR (CDCl ), δ: 1.20 (s, 12 H, Me); 2.53
(sept, 1 H, CH, J = 6.9 Hz); 3.44 (sept, 1 H, CH, J = 6.9 Hz); 6.40
(s, 1 H, Htrop); 7.61—7.67 (m, 1 H, Harom); 7.80—7.82 (m, 2 H,
Harom), 8.18 (d, 1 H, Harom, J = 8.4 Hz); 8.43 (s, 1 H, Harom);
3
(
s, 3 H, Me); 2.64 (s, 3 H, Me); 2.65 (sept, 1 H, CH, J = 6.9 Hz);
3
6
.46 (sept, 1 H, CH, J = 6.9 Hz); 6.45 (d, 1 H, Htrop, J = 1.0 Hz);
.62 (d, 1 H, Htrop, J = 1.0 Hz); 7.39 (d, 1 H, Harom, J = 8.4 Hz);
–
1
19.08 (br.s, 1 H, OH). IR, ν/cm : 3125, 1619, 1600, 1575, 1531,

5,7ꢀDiisopropylꢀ2ꢀquinolylꢀ1,3ꢀtropolone derivatives Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
2467
1
1
7
3
494, 1466, 1417, 1390, 1367, 1355, 1291, 1248, 1183, 1161, 1132,
287 (19), 266 (13), 218 (22), 190 (23), 175 (24), 154 (41), 141 (36),
111, 1091, 1058, 1035, 983, 923, 886, 872, 842, 799. MS (EI,
127 (32), 105 (20), 91 (37), 77 (39), 65 (18), 55 (14), 53 (16). Found
(%): C, 64.64; H, 5.38; N, 6.44. C H ClN O . Calculated (%):
+
0 eV), m/z (Irel (%)): 412 [M] (10), 384 (71), 366 (60), 351 (48),
23
23
2
4
49 (52), 337 (23), 322 (53), 308 (48), 295 (31), 280 (21), 266
C, 64.71; H, 5.43; N, 6.56.
(
1
16), 252 (15), 217 (15), 204 (22), 164 (20), 140 (100), 127 (22),
05 (19), 91 (35), 77 (35), 55 (15). Found (%): C, 63.92; H, 4.98;
N, 6.58. C H ClN O . Calculated (%): C, 64.00; H, 5.13; N, 6.78.
Xꢀray diffraction analysis. The unit cell parameters and the 3D
set of the intensities were obtained using an Xcalibur Eos automated
diffractometer (MoꢀKα radiation, graphite monochromator). Yelꢀ
low transparent crystals of 6g are rhombic, C H24ClNO2,
22
21
2 4
2
ꢀ(4ꢀChloroꢀ6ꢀfluoroquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ1,3ꢀ
2
3
tropolone (6f). Yield 10%. Yellow crystals, m.p. 106—108 °C
M 381.88, a = 10.8322(3), b = 13.0812(4), c = 27.6701(9) Å, V =
i
–1
3
3
(
Pr OH). IR, ν/cm : 3121, 1728, 1643, 1621, 1591, 1496, 1459,
= 3920.8(2) Å , Z = 8, d
= 1.294 g cm , μ(MoꢀKα) =
calc
= 0.15 mm– , space group Pca21. Intensities of 17652 reflections
were collected in the range of angles 2θ < 62.24° in the ω/2θ scan
mode using a single crystal with dimensions 0.4Ѕ0.4Ѕ0.4 mm. After
excluding systematically absent reflections and averaging the inꢀ
1
1
1
409, 1379, 1365, 1349, 1312, 1282, 1245, 1190, 1176, 1149, 1118,
096, 1069, 995, 961, 949, 922, 884, 870, 856, 816. H NMR
1
(
CDCl ), δ: 1.20—1.26 (m, 12 H, Me); 2.69 (sept, 1 H, CH, J =
3
=
6.9 Hz); 3.47 (sept, 1 H, CH, J = 6.9 Hz); 6.58 (d, 1 H, Htrop,
2
2
J = 1.2 Hz); 6.62 (d, 1 H, Htrop, J = 1.2 Hz); 7.46—7.52 (m, 1 H,
tensities of equivalent reflections, complete set of F
and σ(F )
hkl
Harom); 7.77—7.80 (m, 1 H, Harom); 7.87—7.92 (m, 1 H, Harom);
consists of 9481 independent reflections including 8236 reflections
2
2
8
.27 (s, 1 H, Harom); 18.20 (br.s, 1 H, OH). MS (EI, 70 eV), m/z
with F > 4σ(F ). Structure was solved by direct method and reꢀ
+
2
(
Irel (%)): 385 [M] (6), 357 (64), 342 (100), 328 (13), 314 (15),
00 (14), 272 (5), 235 (5), 222 (5), 179 (5), 158 (20), 131 (8), 91
12), 77 (13), 55 (7). Found (%): C, 68.34; H, 5.36; N, 3.48.
C H ClFNO . Calculated (%): C, 68.48; H, 5.49; N, 3.63.
fined by fullꢀmatrix leastꢀsquares against F using SHELXTL proꢀ
3
(
gram package.30 Honꢀhydrogen atoms were refined anisotropically.
All hydrogen atoms of 6g were found by difference Fourier synthesis
of electron density and refined isotropically by leastꢀsquares techꢀ
nique using a riding model.30 In the last cycle of fullꢀmatrix refineꢀ
ment, the absolute shifts for all 487 structure variables were lower
2
2
21
2
2
ꢀ(4ꢀChloroꢀ6ꢀfluoroquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ4ꢀnitroꢀ
1
,3ꢀtropolone (7f). Yield 38%. Yellow crystals, m.p. 175—177 °C
i
–1
(
Pr OH). IR, ν/cm : 3119, 3084, 1647, 1620, 1599, 1572, 1527,
0.001σ. The final divergence factors were as follows: R = 0.0617,
1
1
1
8
497, 1477, 1420, 1386, 1364, 1339, 1283, 1260, 1245, 1147,
123, 1101, 1081, 1055, 1035, 995, 975, 961, 945, 919, 882, 872,
wR = 0.14 for reflections with I > 2σ(I); GOOF = 1.069. At the end
2
of refinement, the final difference Fourier synthesis, the maximum
and minimum peaks of residual electron density were 0.548 and –
0.530 e Å–3, respectively.
1
56, 835. H NMR (CDCl , δ: 1.22 (m, 12 H, Me); 2.73 (spet, 1 H,
3
CH, J = 6.9 Hz); 3.43 (sept, 1 H, CH, J = 6.9 Hz); 6.44 (s, 1 H,
Htrop); 7.52—7.58 (m, 1 H, Harom); 7.80—7.85 (m, 2 H, Harom);
Quantum chemical calculations were performed using hybrid
3
1,32
8
.43 (s, 1 H, Harom); 19.46 (br.s, 1 H, OH). MS (EI, 70 eV), m/z
functional PBE0
and 6ꢀ311+G(d,p) basis set by GAUSSIAN
Irel (%)): 430 [M]+ (4), 402 (29), 384 (28), 369 (23), 354 (11),
09 software. IEFꢀPCM solvation model
33
34,35
was applied for the
(
341 (24), 326 (22), 313 (14), 296 (12), 284 (8), 221 (10), 182 (8),
164 (18), 158 (38), 145 (13), 131 (100), 119 (14), 105(77), 91 (95),
77 (62), 55 (14). Found (%): C, 61.22; H, 4.46; N, 6.38.
calculations in solution employing the solvent parameters for DMSO
(ε = 46.7).
C H ClFN O . Calculated (%): C, 61.33; H, 4.68; N, 6.50.
2
2
20
2
4
This work was financially supported by the National
Foundation for Science and Technology Development of
Vietnam (NAFOSTED) (Grant 104.01ꢀ2015.68), Preꢀ
sidium of the Russian Academy of Sciences (Program
No. 8 "Development of the Chemical Substances Synꢀ
thesis and Design of New Materials", Project No. 007ꢀ
2
ꢀ(4ꢀChloroꢀ8ꢀmethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ1,3ꢀ
tropolone (6g). Yield 24%. Yellow crystals, m.p. 112—114 °C
i
–1
(
Pr OH). IR, ν/cm : 3116, 1635, 1606, 1586, 1560, 1493, 1462,
1420, 1391, 1365, 1349, 1316, 1299, 1286, 1258, 1229, 1192, 1164,
1
1
136, 1110, 1088, 1071, 1066, 1011, 965, 929, 884, 873, 827. H
NMR (CDCl ), δ: 1.19—1.23 (m, 12 H, Me); 2.66 (sept, 1 H, CH,
3
J = 6.9 Hz); 2.74 (s, 3 H, Me), 3.47 (sept, 1 H, CH, J = 6.9 Hz);
0
1114ꢀ16 PR 0256ꢀ2015ꢀ0077), the Russian Foundation
6
7
8
1
3
.49 (d, 1 H, Htrop, J = 1.2 Hz); 6.63 (d, 1 H, Htrop, J = 1.2 Hz);
.47 (t, 1 H, Harom, J = 7.5 Hz); 7.60 (d, 1 H, Harom, J = 7.5 Hz);
for Basic Research (Project No. 14ꢀ03ꢀ00672), the Counꢀ
cil on Grants of the President of the Russian Federation
.00 (d, 1 H, Harom, J = 7.5 Hz); 8.37 (s, 1 H, H
H, OH). MS (EI, 70 eV), m/z (Irel (%)): 381 [M] (4), 353 (65),
), 19.53 (br.s,
arom
+
(
Program for State Support of Leading Scientific Schools,
Grant NShꢀ8201.2016.3). Yu. A. Sayapin is grateful to
Ministry of Education and Science of the Russian Fedꢀ
eration for financial support (State Assignment No. 007ꢀ
01114ꢀ16 PR 0256ꢀ2014ꢀ0009 for 2016).
38 (100), 310 (14), 268 (4), 217 (4), 190 (4), 154 (8), 141 (8), 127
(
8), 91 (9), 77 (10), 55 (5). Found (%): C, 72.14; H, 6.16; N, 3.52.
C H ClNO . Calculated (%): C, 72.34; H, 6.33; N, 3.67.
2
3
24
2
2
ꢀ(4ꢀChloroꢀ8ꢀmethylquinolinꢀ2ꢀyl)ꢀ5,7ꢀdiisopropylꢀ4ꢀnitroꢀ
1
,3ꢀtropolone (7g). Yield 50%. Yellow crystals, m.p. 198—200 °C
i
–1
(
Pr OH). IR, ν/cm : 3130, 1612, 1597, 1586, 1531, 1487, 1466,
References
1
1
418, 1393, 1371, 1291, 1249, 1227, 1167, 1111, 1089, 1060, 1033,
1
015, 987, 931, 892, 873, 846, 835. H NMR (CDCl ), δ: 1.20
3
(
3
s, 12 H, Me); 2.70 (sept, 1 H, CH, J = 6.9 Hz); 2.73 (s, 3 H, Me);
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