Synthesis and structure of 5,7-Di(tert-butyl)-2-(8-methanesulfonyloxyquinolin-2-yl)-1,3-tropolone

Article abstract of DOI:10.1134/S0012500816060082

5,7-Di(tert-butyl)-2-(8-methanesulfonyloxyquinolin-2-yl)-1,3-tropolone whose structure was established by X-ray diffraction analysis and confirmed by ¹H and ¹³C NMR, IR spectroscopy, and mass spectrometry, was obtained by the reaction of 2-methyl-8-methanesulfonyloxyquinoline with 3,5-di(tert-butyl)-1,2-benzoquinone. According to X-ray diffraction study, this sulfonyloxyquinolinotropolone exists in the NH tautomeric form with methanesulfonyloxy group in the exo position to the tropolone ring and the sixmembered chelate ring produced by the quinoline and tropolone moieties stabilized by strong intramolecular hydrogen bond. The strong intramolecular hydrogen bond between the phenolic oxygen atom and the six-membered chelate ring provides supplementary contribution to the stabilization of the NH tautomeric form.

Full text of DOI:10.1134/S0012500816060082

ISSN 0012ꢀ5008, Doklady Chemistry, 2016, Vol. 468, Part 2, pp. 191–194. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © I.E. Mikhailov, A.A. Kolodina, G.A. Dushenko, V.V. Tkachev, S.M. Aldoshin, V.I. Minkin, 2016, published in Doklady Akademii Nauk, 2016, Vol. 468,
No. 6, pp. 652–655.
CHEMISTRY
Synthesis and Structure of 5,7ꢀDi(tertꢀbutyl)ꢀ2ꢀ(8ꢀ
methanesulfonyloxyquinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone
I. E. Mikhailova, b, A. A. Kolodinab, G. A. Dushenkoa, V. V. Tkachevc,
Academician S. M. Aldoshinc, and Academician V. I. Minkinb
Received March 1, 2016
Abstract—5,7ꢀDi(tertꢀbutyl)ꢀ2ꢀ(8ꢀmethanesulfonyloxyquinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone whose structure was
1
established by Xꢀray diffraction analysis and confirmed by H and 13C NMR, IR spectroscopy, and mass
spectrometry, was obtained by the reaction of 2ꢀmethylꢀ8ꢀmethanesulfonyloxyquinoline with 3,5ꢀdi(tert
ꢀ
butyl)ꢀ1,2ꢀbenzoquinone. According to Xꢀray diffraction study, this sulfonyloxyquinolinotropolone exists in
the NH tautomeric form with methanesulfonyloxy group in the exo position to the tropolone ring and the sixꢀ
membered chelate ring produced by the quinoline and tropolone moieties stabilized by strong intramolecular
hydrogen bond. The strong intramolecular hydrogen bond between the phenolic oxygen atom and the sixꢀ
membered chelate ring provides supplementary contribution to the stabilization of the NH tautomeric form.
DOI: 10.1134/S0012500816060082
Chelate ligand systems based on 8ꢀhydroxyquinoꢀ
line and its derivatives are widely used in analytical sulfonyloxyquinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone
chemistry for separation and determination of differꢀ reaction of 2ꢀmethylꢀ8ꢀmethanesulfonyloxyquinoline
ent metal cations [1], for preparation of highly effiꢀ with 3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone via conꢀ
We prepared 5,7ꢀdi(tertꢀbutyl)ꢀ2ꢀ(8ꢀmethaneꢀ
4
by the
2
3
cient photoꢀ and electroluminescent compounds [2, densation of methylene active nitrogen heterocycles
3], highly selective fluorescent chemosensors [4], and with 1,2ꢀbenzoquinones resulting in the expansion of
in medicine due to their high and diverse pharmacoꢀ
logical activity [5]. Good structural variability of this fonyloxyquinolinotropolone
heterocyclic system provides a possibility to design on line ligand system with the 1,3ꢀtropolone moiety in
oꢀquinone ring [9–11]. The alkaline hydrolysis of sulꢀ
4
led to 8ꢀhydroxyquinoꢀ
5
its basis materials with properties useful for practical the second position of the quinoline ring but in higher
applications [6–8]. Therefore, it is an urgent task to total yield (20%) than in the case when 2ꢀmethylꢀ8ꢀ
extend the scope of such compounds, establish their arylsulfonyloxyquinolines were used as initial comꢀ
structure, and study their properties.
pounds (6–11%) [10].
O
O
O
KOH/EtOH
N
O
3
CH3SO2Cl
N
AcOH, 70°C
CH3
N
CH3
OSO2CH3
HO
OH
30 h
OSO2CH3
OH
HO
1
5
4
2
The employment of 2ꢀmethylꢀ8ꢀhydroxyquinoline
1
in this acidꢀcatalyzed reaction instead of its
alkyl(aryl)sulfonyloxy derivatives leads to resinificaꢀ
tion of the initial reagents rather than the target prodꢀ
ucts of type
The structure of sulfonyloxyquinolinotropolone
2
4.
a Southern Scientific Center, Russian Academy of Sciences,
ul. Chekhova 41, RostovꢀonꢀDon, 344006 Russia
4
b Research Institute of Physical and Organic Chemistry,
Southern Federal University, pr. Stachki 194/3,
RostovꢀonꢀDon, 344104 Russia
was established by Xꢀray diffraction analysis and conꢀ
1
firmed by H and 13C NMR, IR spectroscopy, and
mass spectrometry.
c Institute of Problems in Chemical Physics, Russian Academy
of Sciences, pr. Semenova 1, Chernogolovka, Moscow oblast,
142432 Russia
The Xꢀray diffraction data (figure) show that comꢀ
pound
4 exists as an E isomer at the C(2)–C(2') bond
with hydrogen H(1') localization at the N(1') nitrogen
eꢀmail: mikhail@ipoc.rsu.ru
191

192
MIKHAILOV et al.
С(5')
С(4')
С(9)
С(10)
С(11)
С(3')
С(2')
С(4А')
С(8А')
С(6')
С(7')
О(2)
C(3)
C(8)
С(4)
N(1')
С(8')
С(2)
С(5)
О(3)
С(1)
С(7)
О(5)
О(1)
С(6) С(12)
С(13)
S(1)
О(4)
С(14)
С(16)
С(15)
Molecular structure of 5,7ꢀdi(tertꢀbutyl)ꢀ2ꢀ(8ꢀmethanesulfonyloxyquinolinꢀ2ꢀyl)ꢀ1,3ꢀtropolone
4
according to Xꢀray diffraction
study. The O(1)⋅⋅⋅N(1') distance is 2.446(4) Å. Selected bond lengths (Å): O(1)–C(1), 1.307(2); O(2)–C(3), 1.227(2); N(1')–
H(1'), 0.86(1); N(1')–C(2'), 1.340(2); C(1)–C(2), 1.411(2); C(2)–C(3), 1.475(2); C(3)–C(4), 1.497(2); C(4)–C(5), 1.344(2);
C(5)–C(6), 1.455(2); C(6)–C(7), 1.355(2); C(1)–C(7), 1.452(2); C(2)–C(2'), 1.450(2); C(2')–C(3'), 1.431(2). Selected bond
angles (deg): C(1)–O(1)–H(1'), 101.9(1); O(1)–C(1)–C(2), 121.59(16); C(2')–N(1')–H(1'), 118.3(1); C(1)–C(2)–C(2'),
120.16(15);O(2)–C(3)–C(2), 122.31(15); C(1)–C(2)–C(3), 120.09(16); N(1')–C(2')–C(2), 116.44(15).
atom, which leads to the formation of strong intramoꢀ 2.39(1) Å to 2.35(1) Å in quinolinotropolones
lecular hydrogen bond of the N(1')–H(1')⋅⋅⋅O(1) type. respectively. Moreover, the H(1')⋅⋅⋅O(1) distance in
(1.72(1) Å) is longer than in compound (1.64(1) Å)
4 and 5,
4
5
The N(1')–H(1') distance in structure
while H(1')⋅⋅⋅O(1) = 1.72(1) N(1')H(1')O(1) =
149.7(1) , the distance O(1)⋅⋅⋅N(1') = 2.446(4) Å is
0.5 Å shorter than the corresponding van der Waals
contact and is the shortest for all known systems with
strong intramolecular hydrogen bonds of this kind.
The proton of the N–H group producing strong
4 is 0.86(1) Å,
because of the stronger interaction between H(1') and
O(3) in the sulfonyloxy derivative. All these features
Å, ∠
°
lead to supplementary deshielding of the N–H proton
in strongly bound to three heteroatoms in the coorꢀ
4
dination core and to the downfield shift of proton sigꢀ
nal in 1H NMR by 0.52 ppm as compared with comꢀ
pound
5.
intramolecular hydrogen bond in compound
4 is
strongly deshielded and has an extremely downfield
shift in H NMR spectra (CDCl3, 19.03 ppm). The
The 1H NMR spectrum of compound
4
shows proꢀ
1
ton signals of the tropolone ring as two doublets at
6.76 ppm ( = 1.7 Hz) and 6.66 ppm ( = 1.7 Hz),
sixꢀmembered ring of the strong intramolecular
hydrogen bond, quinoline fragment, and C(1)–C(3),
C(7) atoms of the tropolone ring lie in the common
plane (with slight deviations for the C(7) atom), while the
tropolone ring is slightly distorted at the C(3)–C(7) line
(dihedral angle between the C(3)C(2)C(1)C(7) and
J
J
while the signal of the proton in the 3'ꢀposition of the
quinoline ring is shifted downfield (8.15 ppm) as comꢀ
pared with the corresponding signal in the spectrum of
initial quinoline 2 (7.33 ppm). The signal of the N–H
proton producing strong intramolecular hydrogen
bond with the tropolone oxygen that closes the sixꢀ
membered chelate ring is observed in the downfield
region at 19.03 ppm as a narrow singlet peak.
C(4)C(5)C(6)C(7) planes is 30.3(15)
Quinolinotropolone [10] has a similar structure
where phenolic hydroxyl like methanesulfonyloxy
group in compound is located in the exo position to
°).
5
4
13C NMR spectrum of compound
4 shows 21 sigꢀ
the tropolone moiety; however, the replacement of
phenolic group proton by the methanesulfonyl substitꢀ
uent leads to the enhancement of interaction between
nal, including signals at 30.4, 31.5 ppm and 37.6,
38.8 ppm from the methyl groups and quaternary carꢀ
bon atoms of the tertꢀbutyl substituents, respectively.
Fourteen signals of the tropolone ring and quinoline
moiety appear in the region 115.5–157.3 ppm, while
the signals of the carbonyl carbons of tropolone
the phenolic oxygen and the N–H proton in
4 as comꢀ
pared with structure . This is evidenced by a decrease
5
in the C(8A')N(1')H(1') and N(1')H(1')O(1) angles
from 124.2(1)° and 146.1(1)° to 118.3(1)° and
140.7(1)°, as well as the H(1')⋅⋅⋅O(3) distances from emerge at 174.3 and 195.4 ppm. The 1H and 13C NMR
DOKLADY CHEMISTRY Vol. 468
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2016

SYNTHESIS AND STRUCTURE
193
dcalcd = 1.318 g/cm3, space group Pꢀ1. Intensities of
8419 reflections were measured in the angle range
spectra, the IR spectrum that displays characteristic bands
of NH (3019–3069 cm–1), C=O (1620, 1637 cm–1) and
SO2 groups (1182, 1346 cm–1), and mass spectrum
(
2
θ ≤ 53
of equivalent reflections, the working body of meaꢀ
sured F 2 F 2
hkl and consisted of 4738 indepenꢀ
dent reflections, of which 3782 with F 2 F 2
. The
°) by w scanning. After averaging of intensities
confirm the structure of compound
4.
(
)
σ(
)
Compound can exist also in the OH tautomeric
4
> 4σ( )
form resulting from intramolecular proton transfer
from the pyridine nitrogen to the nearest carbonyl
oxygen of tropolone. According to DFT B3LYP/6ꢀ
311++G(d,p) quantum chemical computations for
the gas phase with the use of Gaussianꢀ09 program,
these tautomeric forms correspond to minima on the
potential energy surface. It was found that the NH
form (EZPE = –1799.03048 au, ω1 = 17 cm–1), whose
geometrical parameters agree well with Xꢀray diffracꢀ
tion data, is only 0.6 kcal/mol more stable than the
corresponding OH form (EZPE = –1799.02955 au,
structure was solved by direct methods and refined by
fullꢀmatrix least squares on F2 in the anisotropic
approximation for nonꢀhydrogen atoms (hydrogen
atoms were refined in the isotropic approximation as
riding on their bonded atoms) with the use of the
SHELXTL software [12]. The final refining parameꢀ
ters for compound R1 = 0.045 for all observed reflecꢀ
4:
tions with ≥ 2σ(i) and R1 = 0.061 for all measured
I
reflections, GOF = 1.040. Full tables of atomic coorꢀ
dinates, bond distances, bond angles, and thermal
ω1 = 14 cm–1), which does not exclude the presence of
the OH form in solutions.
parameters of compound
4 are available from the
authors on request (vatka@icp.ac.ru).
Initial compounds used were commercially availꢀ
Thus, the new precursor of the polydentate 8ꢀhydroxꢀ
yquinoline ligand system with the 1,3ꢀtropolone moiety
in the 2ꢀposition of the heterocyclic ring was prepared
by the reaction of 2ꢀmethylꢀ8ꢀmethanesulfonyloxꢀ
yquinoline with 1,2ꢀbenzoquinone. It was shown that
in crystal state it exists in the NH tautomeric form with
methanesulfonyloxy group in the exo position to the
tropolone ring, which is stabilized due to emergence of
supplementary intramolecular hydrogen bond
between the phenolic oxygen and the sixꢀmembered
chelate ring formed by the quinoline and tropolone
moieties.
able 2ꢀmethylꢀ8ꢀhydroxyquinoline
nyl chloride, and 3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoꢀ
quinone from Aldrich.
1, methanesulfoꢀ
3
2ꢀMethylꢀ8ꢀmethanesulfonyloxyquinoline 4. A soluꢀ
tion of 1.4 mL (0.18 mmol) of methanesulfonyl chloꢀ
ride in 10 mL of dry benzene was added dropwise on
stirring to a solution of 2.4 g (15 mmol) of 2ꢀmethylꢀ
8ꢀhydroxyquinoline
1 and triethylamine (3.5 mL) in
20 mL of dry benzene at ambient temperature. The
reaction mixture was kept at ambient temperature for
one day and next heated under reflux for 1 h. After
removal of the solvent on a water bath, the oily residue
was cooled to ambient temperature and 50 g of
crushed ice was added. The resulting white powder was
EXPERIMENTAL
1H and 13C NMR spectra in CDCl3 were recorded
at 22°C on a Bruker DPXꢀ250 spectrometer operating
separated by filtration, washed with cold water (2
×
15 mL), dried in air, and crystallized from ethanol.
Colorless crystals, yield 3.36 g (95%), mp 114–116°C.
at 250.13 and 62.90 MHz, respectively. Chloroform
signals (δH = 7.24 ppm, δС = 77.00 ppm) were used as
an internal reference. IR spectra were recorded as thin
films on a Varian Excalibur 3100 FTꢀIR spectrophoꢀ
tometer. Mass spectra were obtained on a Finnigan
MAT INCOS 50 spectrometer by electron impact
(ionizing voltage 70 eV). Elemental analysis was carꢀ
ried out on a KOVO CHN analyzer. Chromatography
was conducted on columns filled with Brockmann
activity grade II or III Al2O3. Melting points were
determined on a Boetius hot stage apparatus.
IR (thin film,
1585, 1508, 1346 (SO2), 1314, 1182 (SO2).
ν
, cm–1): 1648 (C=N), 1629, 1607,
1H NMR (СDCl3,
, ppm, , Hz): 8.07 (d, 1H,
8.5, Hquinol), 7.72 (dd, 1H, = 8.2, 1.3, Hquinol), 7.64
(dd, 1H, = 8.0, 1.3, Hquinol), 7.46 (dd, 1H, = 8.0,
7.9, Hquinol), 7.33 (d, 1H, = 8.5, Hquinol), 3.48 (s, 3H,
SO2CH3), 2.73 (s, 3H, CH3).
13C NMR (CDCl3,
, ppm): 160.4, 145.6, 141.3,
136.6, 128.5, 127.3, 125.8, 124.2, 123.4, 39.7, 25.9.
MS (EI, 70 eV,
rel, %)): 237 (M+, 22), 159
δ
J
J =
J
J
J
J
δ
Xꢀray diffraction data. Unit cell parameters for
crystal and 3D set of intensities for compound 5 were
obtained on an Xcalibur, Eos automated diffractomeꢀ
ter (MoKα radiation, graphite monochromator, 100 K).
Yellow monoclinic crystals, chemical formula
m/z (I
(100), 130 (75), 103 (23), 77 (25), 63 (11), 51 (11),
39 (10).
For C11H11NO3S anal. calcd. (%): C, 55.69;
H, 4.64; N, 5.91.
C25H29NO5S,
11.3680(5),
95.955(4)
M
= 455.55;
= 18.1682(9)
= 103.149(4)
a
= 5.8144(3) Å,
= 97.648(4)
= 1147.5(1) Å3
b
β
= 2,
=
=
c
γ
Å,
α
°
,
°,
°,
V
,
Z
Found (%): C, 55.77; H, 4.58; N, 6.17.
DOKLADY CHEMISTRY Vol. 468
Part 2 2016

194
MIKHAILOV et al.
5,7ꢀDi(tertꢀbutyl)ꢀ2ꢀ(8ꢀmethanesulfonyloxyquinoꢀ with water (3
× 30 mL) and recrystallized from toluꢀ
linꢀ2ꢀyl)ꢀ1,3ꢀtropolone 4. A mixture of 1.18 g (5 mmol) ene. Yield 0.36 g (87%), yellow crystals, mp 257–
of 2ꢀmethylꢀ8ꢀmethanesulfonyloxyquinoline and 258 C (lit.: 257–258 C [10]).
2.11 g (10 mmol) of 3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoꢀ
quinone in 5 mL of AcOH was kept at 65–67°C for
2
°
°
3
ACKNOWLEDGMENTS
60 h (TLC monitoring). After reaction completion,
the reaction mixture was diluted with cold water
(250 mL) and extracted with CH2Cl2 (3 × 30 mL). The
organic fraction was dried with Na2SO4 and CH2Cl2
was removed. The product was isolated by column
chromatography (Al2O3 sorbent, light petroleum ether +
This work was supported through grant
no. 213.01–2014/005VG from the Southern Federal
University (V.I. Minkin, A.A. Kolodina) and State
project for 2016 no. 007–01114–16 PR 0256–2014–
0009 (I.E. Mikhailov, G.A. Dushenko).
CH2Cl2 (1 : 1) as an eluent), yellow fraction with Rf
=
0.33 was collected. After removal of the solvent, the
solid residue was recrystallized from propanꢀ2ꢀol. Yelꢀ
REFERENCES
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low crystals, yield 1.09 g (24%), mp 218–219
°C.
IR (thin film,
ν
, cm–1): 3069–3019 (NH), 1637,
1620 (C=O); 1603, 1580, 1565, 1504, 1461, 1395,
1346 (SO2), 1235, 1182 (SO2), 1157, 1066, 1048, 868,
803, 754.
,
1H NMR (CDCl3,
OH), 8.15 (d, 1H, = 9.3, Hquinol), 8.07 (d, 1H,
9.3, Hquinol), 7.74 (d, 1H, = 7.9, Hquinol), 7.69 (d, 1H,
= 7.9, Hquinol), 7.47 (dd, 1H, = 7.9, 7.9, Hquinol),
= 1.7, Htrop), 6.66 (d, 1H, = 1.7, Htrop),
δ, ppm, J, Hz): 19.03 (s, 1H,
J
J =
J
5. Shults, M.D., Pearce, D.A., and Imperiali, B., J. Am.
Chem. Soc., 2003, vol. 125, no. 35, pp. 10591–10597.
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J
J
6.76 (d, 1H,
J
J
3.46 (s, 3H, CH3), 1.38 (s, 9H, C(CH3)3), 1.24, (s, 9H,
C(CH3)3).
13C NMR (CDCl3,
δ, ppm): 195.4, 174.3, 157.3,
155.8, 154.7, 141.0, 137.6, 135.0, 127.6, 126.7, 126.0,
125.2, 124.0, 123.5, 121.7, 115.5, 39.3, 38.8, 37.6, 31.5
(3C), 30.4 (3C).
MS (EI, 70 eV, m/z (I
rel, %)): 427 (M+–CO, 42),
412 (27), 384 (16), 332 (22), 318 (19), 292 (14), 248
(9), 204 (8), 156 (12), 105 (9), 91 (20), 79 (84), 57
(95), 41 (100).
For C31H33NO5S anal. calcd. (%): C, 70.03; H,
6.26; N, 2.63.
Found (%): C, 69.92; H, 6.33; N, 2.77.
5,7ꢀDi(tertꢀbutyl)ꢀ2ꢀ(8ꢀhydroxyquinolinꢀ2ꢀyl)ꢀ1,3ꢀ
tropolone 5. A solution of KOH (1 M, 3.0 mL) was
added to a solution of 0.50 g of compound 4 in 15 mL
of ethanol and heated under reflux on a water bath for
20 h. The reaction mixture was cooled to ambient
temperature, diluted with 40 mL of water, acidified to
neutral pH with 0.1 M HCl solution, the resulting yelꢀ
low precipitate was separated by filtration, washed
Translated by I. Kudryavtsev
DOKLADY CHEMISTRY Vol. 468
Part 2
2016