Spiropyrans and spirooxazines : 444. Synthesis and spectral properties of 6'-halo-substituted spiro[indoline-2,2'-2H-pyrano[3,2-h]quinolines]

Article abstract of DOI:10.1007/s11172-008-0022-y

The Duff formylation of 5-bromo- or 5-chloro-8-hydroxyquinoline leads to the corresponding 7-formyl derivatives, condensation of which with 2-methyleneindolines or 3H-indolium halides in the presence of a base afforded new photochromic 6'-halo-substituted spiro[indoline-2,2'-2H- pyrano[3,2-h]quinolines]. Thermal and photo-induced isomerization of compounds obtained have been investigated by 1H NMR and UV spectroscopy.

Full text of DOI:10.1007/s11172-008-0022-y

Russian Chemical Bulletin, International Edition, Vol. 57, No. 1, pp. 151—158, January, 2008
151
Spiropyrans and spirooxazines
4.* Synthesis and spectral properties
of 6´ꢀhaloꢀsubstituted spiro[indolineꢀ2,2´ꢀ2Hꢀpyrano[3,2ꢀh]quinolines]
a
b
b
b
N. A. Voloshin,a A. V. Chernyshev,b S. O. Bezuglyi, A. V. Metelitsa, E. N. Voloshina, and V. I. Minkin

аSouth Scientific Center, Russian Academy of Sciences,
41 ul. Chekhova, 344006 RostovꢀonꢀDon, Russian Federation
bScientific Research Institute of Physical and Organic Chemistry, South Federal University,
194/2 prosp. Stachki, 344090 RostovꢀonꢀDon, Russian Federation.
Fax: +7 (863) 243 4667. Eꢀmail: photo@ipoc.rsu.ru
The Duff formylation of 5ꢀbromoꢀ or 5ꢀchloroꢀ8ꢀhydroxyquinoline leads to the corresponding
7ꢀformyl derivatives, condensation of which with 2ꢀmethyleneindolines or 3Нꢀindolium halides in
the presence of a base afforded new photochromic 6´ꢀhaloꢀsubstituted spiro[indolineꢀ2,2´ꢀ2Hꢀ
pyrano[3,2ꢀh]quinolines]. Thermal and photoꢀinduced isomerization of compounds obtained have
been investigated by 1Н NMR and UV spectroscopy.
Key words: formylquinolinols, spiroindolinepyranoquinolines, photochromism.
Scheme 1
Elaboration and synthesis of polyfunctional molecuꢀ
lar systems nowadays is under intensive research, this
field is important for the development of molecular elecꢀ
tronics and sensors.2,3 Bistable photochromic comꢀ
pounds (spiropyrans, spirooxazines, chromenes), conꢀ
taining a cationꢀreceptor center, are typical examples of
such molecules.
Photochromism of spiropyrans of the type A (Scheme
1) is caused by thermally and photochemically reversible
process of heterolytic cleavage of the Сspiro—О bond and
subsequent cisꢀtransꢀisomerization to metastable meroꢀ
cyanine form В.4,5
The presence of partial negative charge on the oxygen
atom of the merocyanine isomer makes it a potential
ligand in the complexꢀforming reactions with metal
ions,6—8 as well as with a number of organic substrates.9,10
Compounds of this class were first represented by
spiroindolinepyranoquinolines.11,12 In these compounds,
both photochromic and coordination functions are inteꢀ
grated. Recently, it was shown13—16 that spiroindolineꢀ
pyranoquinolines are efficient photodynamic fluorescent
chemosensors for a number of metal cations.
In the present work, in continuation of our research
on fluorescent chemosensors on the basis of spiropyrans,
we report the synthesis of 5ꢀhaloꢀsubstituted 7ꢀformylꢀ
8ꢀhydroxyquinolines, as well as the synthesis and analyꢀ
sis of the photochromic properties of 6´ꢀhaloꢀsubstiꢀ
tuted spiroindolinepyranoquinolines.
Synthesis of 6´ꢀhaloꢀsubstituted spiroindolineꢀ
pyranoquinolines. 6´ꢀHaloꢀsubstituted spiroindolineꢀ
pyranoquinolines were synthesized according to Scheme
2. The reaction of 2ꢀmethyleneindolines 5 and 6 or 3Нꢀ
indolium halides 7—10 with 5ꢀhaloꢀsubstituted formylꢀ
quinolinols 3 and 4 in the presence of a base afforded
unsubstituted spiroindolinepyranoquinolines 1111 and
1215 and new spiroindolinepyranoquinolines 13—22, conꢀ
taining various substituents in the indoline fragment of the
molecule.
* For Part 3, see Ref. 1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 146—153, January, 2008.
1066ꢀ5285/08/5701ꢀ0151 © 2008 Springer Science+Business Media, Inc.

152
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
Voloshin et al.
Scheme 2
The structures of compounds obtained were estabꢀ
lished by Н NMR spectroscopy and confirmed by elꢀ
1
emental analysis data.
Spectral and photochemical investigations. Soluꢀ
tions of spiropyrans 11—18, 21, and 22 in polar solvents,
in contrast to their solutions in nonpolar solvents, have
a noticeable violet color, caused by the presence of
merocyanine isomers В, which are in equilibrium with
1
cyclic isomers А (see Scheme 1). Н NMR spectroscopy
is one of the most convenient methods for the study of the
ringꢀchain
equilibrium
spiropyranꢀmerocyanine
(А
В). Analysis of the 1Н NMR spectra allows one
to establish the geometrical structure of the openꢀchain
and cyclic forms of the spiro compound. When the openꢀ
chain form and the cyclic one are both presented in
a solution, the method allows one to determine their
ratio, since signals of such characteristic (indicator) fragꢀ
ments, as gemꢀdimethyl group, Nꢀalkyl substituent, and
protons of the double С(3)=С(4) bond usually can be
easily identified and they have different chemical shifts for
the cyclic (А) and openꢀchain (B) forms.18—21
According to 1Н NMR spectroscopy, spiropyrans 11—
18 and 21, 22 exist in the solution (CDCl3 for compounds
11—18 and DMSOꢀd6 for compounds 21 and 22) as
a mixture of isomeric spirocyclic (А) and merocyanine
(В) forms, the ratio of which depends on the nature of
substituents in the indoline fragment of the molecule.
Signals of 3´ꢀН and 4´ꢀН protons of the spirocyclic form
reveal themselves as two doublets at 5.76—5.84 ppm (5.91—
5.94 ppm for compounds 21 and 22) and 6.81—6.89 ppm
(7.13—7.15 ppm for compounds 21 and 22), respectively
(J = 10.2 Hz). Signals of the corresponding vinyl 4´ꢀН
and 3´ꢀН protons of the merocyanine form of compounds
15 and 16 (ratio of the spirocyclic and merocyanine forms
for them is ~1 : 1) are located at 6.69—6.70 and 6.87—
6.89 ppm, respectively (J = 14.0 Hz). Signals of the gemꢀ
dimethyl group of the spirocyclic form reveal themselves
as two threeꢀproton singlets at 1.18—1.30, 1.31—1.38 ppm
for compounds 11—18 and at 1.06—1.09, 1.17—1.19 ppm
for compounds 21 and 22. Signals of the gemꢀdimethyl
group of the merocyanine form of the spiropyrans 15 and
16 reveal themselves as sixꢀproton singlet at 1.71—
1.73 ppm. Signal of the Nꢀmethyl substituent of comꢀ
pounds 11—16 is located in the interval 2.72—2.79 ppm
(spirocyclic form) and at 3.53—3.55 ppm in case of
merocyanine form of spiropyrans 15 and 16.
Comꢀ
pound
R1
R2
X
7
8
9
10
Me
CH2Ph
CH2CH2COOH
CH2CH2OH
OC16H33
I
I
I
H
H
H
Br
Comꢀ
pound
11
12
13
14
15
16
17
18
R1
R2
R3
Me
Me
Me
Me
Me
Me
CH2Ph
CH2Ph
H
H
Cl
Cl
Br
Cl
Br
Cl
Br
Cl
Br
Cl
Br
Cl
Br
Cl
OC16H33
OC16H33
H
H
H
H
H
H
19
20
21
22
CH2CH2OH
CH2CH2OH
CH2CH2COOH
CH2CH2COOH
1
According to Н NMR spectroscopy, compounds 19
and 20, in contrast to spiropyrans 11—18, 21 and 22,
exist as a mixture of (hydroxystyryl)oxazolidinoindolines,
presented in the transꢀform (С), spirocyclic form (А),
and insignificant amount of Вꢀform (Scheme 3).
Signals of 3´ꢀН and 4´ꢀН of the spirocyclic form of
compounds 19 and 20 are located at 5.75 and 6.86 ppm
(J = 10.2 Hz), signals of the corresponding vinyl protons
In contrast to the multiꢀstep synthesis of 7ꢀformylꢀ8ꢀ
hydroxyquinoline described in the literature13 (direct
formylation of 8ꢀhydroxyquinoline leads to 5ꢀformyl deꢀ
rivative17), 5ꢀhaloꢀsubstituted formylquinolinols 3 and
4 were obtained by the Duff formylation of the correꢀ
sponding quinolinols 1 and 2.

6´ꢀHalospiro[indolinepyranoquinolines]
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
153
Scheme 3
of the oxazolidine form are located at 6.50 and 7.29 ppm
(J = 16.0 Hz), which is in agreement with the data for
similar oxazolidine derivatives.22 Signals of the gemꢀdiꢀ
methyl group of compounds 19 and 20 reveal themselves
as two threeꢀproton singlets at 1.18—1.20 and 1.33—
1.34 ppm (spirocyclic form) and at 1.20—1.22 and 1.47—
1.49 ppm in case of the oxazolidine form.
1.2
1.0
0.8
0.6
Table 1. Absorption spectra characteristics (λ/nm, ε/L mol–1 cm–1
and observed times (τ/s) of thermal relaxation processes of
spiropyrans 11—22 at 293 K
)
0.4
0.2
Comꢀ
pound
Toluene
Chloroform
Fig. 1. Photoꢀinduced changes of the absorption spectrum of
spiropyran 11 in acetonitrile (С11 = 4.9•10–5 mol L–1, Т = 293 К;
irradiation with light of λ = 365 nm, the interval between the spectra
is 0.5 s).
abs
abs
max
(B)
abs
λ
ε
λ
τ
λ
ε
max
max
(A)
(B)
11
12
13
14
15
16
17
18
19
20
21
22
343
4740
4600
4900
4740
4870
4930
4590
4490
6370b
7070b
—
560
598
559
598
561
597
560
597
570
607
567
607
561
598
561
598
2.8
3.1
3.6
2.4
2.7
3.1
6.0
3.6
—
566
605
566
605
568
607
567
607
573
616
573
614
567
607
567
607
569
603
569
606
568
607
568
608
48700
50750
52700
52600
Signals of the ring protons of the indoline and quinoꢀ
line fragments of the spirocyclic and merocyanine forms
and of the ring protons of the quinoline fragment of the
spirocyclic and oxazolidine forms of these compounds
also differ in values of their chemical shifts.
343
342
341
342
343
343
342
a
—
—
—
—
a
a
Cyclic isomers А of spiropyrans 11—18, 21, and 22
are characterized by the longꢀwave absorption bands with
maxima at 341—343 nm and their molar absorption coꢀ
efficient values (ε) of 4490—4930 mol L–1 cm–1, position
and intensity of which virtually are independent of subꢀ
stituents R1, R2, and R3 (Table 1, Fig. 1).
a
50400
64200
52000
64300
a
—
—
—
—
—
—
—
—
a
1
According to the Н NMR data, compounds 19 and
a
20 exist in solutions as an equilibrium mixture of
spirocyclic, merocyanine, and oxazolidine (С) forms
with the latter being a predominant component. Thereꢀ
fore, positions and intensities of the longꢀwave absorpꢀ
tion of oxazolidine isomers can be estimated from the
absorption characteristics of spiropyrans 19 and 20 soluꢀ
tions: the absorption maxima are located at 336 nm with
the molar absorption coefficient ε = 6370 (19) and
7060 mol L–1 cm–1 (20) (see Table 2).
a
337b
336a
—
c
a
a
c
a
—
—
a
d
—
—
—
—
—
—
—
—
d
—
—
—
In polar solvents, such as acetonitrile or chloroform,
an increase in intensities of the structured longꢀwave
absorption bands of spiropyrans 11—18, 21, and 22 soꢀ
lutions, characteristic of acyclic merocyanine isomers B
a The equilibrium concentration of form B is insufficient for the
determination of ε value. b Oxazolidine form (C). c Spiropyrans do
not show photochromic properties at room temperature. d The
substance is insoluble in toluene.

154
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
Voloshin et al.
Table 2. Chemical shifts (δ) of the protons in positions 7´, 8´, and 9´ of the indolinepyranoquinoline fragment
of spiropyrans 11—22 for different isomeric form and the content of acyclic isomers of spiropyrans at 293 K
Comꢀ
pound
Solꢀ
vent
Cyclic form (A)
H(8´)
Openꢀchain form (B)
СB
(%)
H(7´)
H(9´)
H(7´)
H8´
H(9´)
11
12
13
14
15
16
17
18
20
19
21
22
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
8.35
8.39
8.36
8.40
8.35
8.41
8.36
8.40
8.39
8.37
8.33
8.41
7.37
7.43
7.39
7.39
7.37
7.40
7.39
7.39
7.39
7.41
7.57
7.60
8.77
8.80
8.80
8.82
8.76
8.82
8.79
8.81
8.78
8.76
8.75
8.80
8.15
8.18
8.16
8.18
8.15
8.21
8.13
8.16
8.46*
8.43*
8.14
8.20
7.46
7.48
7.48
7.49
7.45
7.49
7.45
7.47
7.51*
7.52*
7.60
7.60
8.74
8.78
8.75
8.78
8.74
8.79
8.73
8.76
8.79*
8.79*
8.66
8.72
24.6
23.7
9.3
9.0
49.2
49.5
16.4
13.7
84.3*
84.4a
15.2
15.3
CDCl3
DMSOꢀd6
DMSOꢀd6
* Oxazolidine form (C).
Table 3. Thermodynamic parameters (∆H, ∆G/kJ mol–1 and
is observed in the spectral region 522—620 nm (see Table
1). This indicates an increase in concentration of acyclic
isomers B due to the shift of equilibrium in the ground
state between spirocyclic and merocyanine forms. The
intensity of the longꢀwave absorption bands of the
merocyanine forms of spiropyrans in chloroform, calcuꢀ
lated from the equilibrium composition, is characterized
by ε values equal to 50750—64300 L mol–1 cm–1 in the
maxima.
∆S/J mol–1 L–1) of thermal equilibrium А
of spiropyrans 11 and 12 at 293 K
B in solutions
Comꢀ
pound
Solꢀ
vent
K•102
∆H°
∆G°
∆S°
11
Toluene
1.7
8.4
33.0
1.1
6.6
31.0
—*
6.2
—*
6.0
—*
0.7
Acetonitrile
Chloroform
Toluene
Acetonitrile
Chloroform
Introduction of an alkoxy substituent in position 5 of
the indoline fragment of spiropyrans causes the most
significant changes in the spectral characteristics of
merocyanine isomers B out of all the R1, R2, and R3
substituents. Such an introduction results in the bathoꢀ
chromic shift of the longꢀwave absorption maxima for
the solutions of compounds 15 and 16, as well as in the
increase of molar absorption coefficient as compared
with unsubstituted spiropyrans 11 and 12 (see Table 1).
Position of the spiropyran—merocyanine equilibrium
depends only slightly on the nature of halogen atom in
position 6´ (Table 2). At the same time, substituents in
the indoline part of the molecule significantly shift posiꢀ
tion of the equilibrium. Thus, πꢀdonor alkoxy substituꢀ
ent in position 5 assists in delocalization of the partial
positive charge in the indoline fragment, thus increasing
relative stability of the merocyanine form, in contrast to
5ꢀchloroꢀ and 1ꢀbenzylꢀsubstituted spiropyrans, which
show significantly lower equilibrium content of the openꢀ
chain form (see Table 2). In case of 1ꢀ(2ꢀhydroxyethyl)
derivatives, the basicity of the hydroxy oxygen atom,
obviously, is higher than that of oxygen atom of the quinoꢀ
lone fragment of the merocyanine form, therefore, the
cyclization of the latter proceeds with predominant forꢀ
mation of the oxazolidine ring and, to a lesser extent, of
the pyran one, which leads to the observed shift of equiꢀ
librium in the ground state toward oxazolidine form С.
12
—*
5.4
—*
4.2
—*
4.1
*The relationship of observed equilibrium constant K versus temꢀ
perature does not obey the Vant Hoff law.
In polar solvents, the equilibrium in solutions of
spiropyrans under study is shifted toward merocyanine
form В. The equilibrium constants K for the solutions of
lnK
–2.5
–2.6
–2.7
–2.8
1
2
3.35
3.40
3.45
3.50
3.55 T –1•103/K–1
Fig. 2. Logarithm of equilibrium constant (K) of cyclic (A) and
merocyanine (B) forms of spiroсpyrans 11 (1) and 12 (2) in acetoꢀ
nitrile versus reciprocal temperature.

6´ꢀHalospiro[indolinepyranoquinolines]
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
155
lnK
spiropyrans 11 and 12 in acetonitrile and chloroform are
higher than in toluene (Table 3).
1
–1
–2
–3
–4
–5
–6
The equilibrium constant А
B increases with
2
3
4
the increase of polarity of the solvents (see Table 3).
A linear plot of the logarithms of the equilibrium conꢀ
stants of the cyclic and merocyanine forms of spiropyrans
11 and 12 versus reciprocal temperature is presented in
Figure 2. Analysis of the relationship of the equilibrium
constants versus temperature in acetonitrile applying the
Vant Hoff equation allowed us to determine thermo
dynamic parameters of the equilibrium А
B and on
the basis of the standard enthalpy ∆H° values to estimate
the difference between the ground state levels of the cyclic
and merocyanine isomers, which are equal to 6.2 and
5.4 kJ mol–1 for spiropyrans 11 and 12, respectively (see
Table 3).
When the spiropyran solutions are irradiated in the
longꢀwave absorption bands, they acquire a color, which
is caused by the increase of intensities of absorption bands
of acyclic forms B (see Table 1, Fig. 1). After the irradiaꢀ
tion is discontinued, a thermal discoloration is observed,
resulting in the restoration of the initial equilibrium. The
thermal relaxation processes are satisfactory described
by the monoexponential function with the observed time
constants being in the range τ = 2.4—6.0 s at 293 K (see
Table 1).
3.35
3.40
3.45
3.50
3.55
T –1•103/K–1
Fig. 3. Logarithms of the rate constant of the forward (kAB) (1, 2)
and reverse (kBA) (3, 4) reactions of thermal isomerization of
spiropyrans 11 (1, 3) and 12 (2, 4) in acetonitrile versus reciprocal
temperature.
In toluene, spiropyrans 11 and 12 are found to deviate
from the Vant Hoff and Arrhenius laws. In our opinion,
most likely this caused by the fact that in toluene a deꢀ
crease in temperature creates conditions for the stabiliꢀ
zation of more than one transoid isomer of the meroꢀ
cyanine form.20,21 Since absorption spectra of the transoid
isomers differ only slightly,23 a mistake occurs during the
kinetic analysis of the overlapped absorption bands on
the analytical wave lengths, which leads to the aforemenꢀ
tioned deviations.
On the basis of the equilibrium constants K and the
thermal relaxation time constants τ values for spiropyrans
In conclusion, a oneꢀstep synthesis of 5ꢀhaloꢀsubstiꢀ
tuted 7ꢀformylꢀ8ꢀhydroxyquinolines by the Duff formylꢀ
ation of 5ꢀbromoꢀ or 5ꢀchloroꢀ8ꢀhydroxyquinolines has
been proposed, on the basis of which new photochromic
6´ꢀhaloꢀsubstituted spiroindolinepyranoquinolines have
been synthesized. Thermochromic and photochromic
properties of the synthesized compounds have been studꢀ
ied. Nꢀ(2ꢀHydroxyethyl)ꢀsubstituted spiropyrans, in
contrast to the other spiropyrans, were found to exist in
solutions as an equilibrium mixture of three isomeric
forms: spirocyclic, merocyanine, and oxazolidine ones.
11 and 12, the rate constants for the forward А → B (kAB
)
and the reverse B → А (kBA) thermal reactions were deterꢀ
mined. It should be noted that going from toluene to
acetonitrile, the rate constants of the thermal ring openꢀ
ing increase, whereas the rate constants of the thermal
cyclization decrease (Table 4). For the rate constants of
the thermal processes in acetonitrile kBA and kAB, the
Arrhenius type relationship versus temperature is obꢀ
served (Fig. 3), which allowed us to determine the activaꢀ
tion energy for the thermal reactions of coloration and
discoloration (see Table 4).
Experimental
Table 4. Kinetic parameters of the forward and reverse thermal
1Н NMR spectra were recorded on a Varian Unityꢀ300
spectrometer (300 МHz) at 20 °C, δ values were determined to
within 0.01 ppm, spinꢀspin coupling constants, within 0.1 Hz.
Electronic absorption spectra were recorded on a Varian Caryꢀ100
spectrometer. Irradiation of the samples was carried out by the
highꢀpressure mercury lamp DRShꢀ250, supplied with a set of
interferential light filters for the selection of the mercury spectrum
lines. Time constants of the processes of thermal discoloration τ
were calculated using the equation
reactions of spiropyrans 11 and 12: the rate constant values
ВА
(kАВ, kВА) at 292 K and activation energy values (EaАВ, Ea
)
АВ
BA
Compoꢀ Solꢀ
kАВ•102 kBA•102 Ea
Ea
und
vent
s–1
kJ mol–1
11
12
Toluene
Acetonitrile
Toluene
0.6
1.4
0.3
1.4
35.5
16.4
31.7
20.4
—*
90.6
—*
—*
86.4
—*
Acetonitrile
92.2
87.2
ln(At – Ae) = –t/τ + ln(A0 – Ae),
* The relationship of kAB and kBA for spiropyrans in toluene versus
temperature does not obey the Arrhenius law.
where A0, At, and Ae are the initial, current, and equilibrium
absorbance values. Rate constants of the forward and reverse proꢀ

156
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
Voloshin et al.
8.35 (dd, 1 Н, Н(7´), J = 8.6 Hz, J = 1.6 Hz); 8.77 (dd, 1 Н, Н(9´),
J = 4.2 Hz, J = 1.7 Hz).
cesses were calculated using the correlations
6´ꢀChloroꢀ1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ2Hꢀpyraꢀ
no[3,2ꢀh]quinoline] (12). The yield was 72%, m.p. 177—178 °C
(from heptane) (cf. Ref. 16: m.p. 137—141 °C). Found (%): C,
72.90; H, 5.45; N, 7.83. C22H19ClN2O. Calculated (%): C, 72.82;
H, 5.28; N, 7.72. 1H NMR (CDCl3), δ: 1.19 (s, 3 H, С(3)Ме); 1.34
(s, 3 H, С(3)Ме); 2.79 (s, 3 H, 1ꢀМе); 5.79 (d, 1 H, Н(3´), J =
10.2 Hz); 6.52 (d, 1 Н, Н(7), J = 7.7 Hz); 6.82 (dt, 1 H, H(5), J =
7.4 Hz, J = 0.9 Hz); 6.87 (d, 1 H, Н(4´), J = 10.2 Hz); 7.06 (dd, 1 H,
H(4), J = 7.3 Hz, J = 0.9 Hz); 7.15 (dt, 1 H, H(6), J = 7.7 Hz,
J = 1.2 Hz); 7.33 (s, 1 Н, Н(5´)); 7.43 (dd, 1 H, H(8´), J = 8.6 Hz,
J = 4.2 Hz); 8.39 (dd, 1 Н, Н(7´), J = 8.6 Hz, J = 1.7 Hz); 8.80 (dd,
1 Н, Н(9´), J = 4.2 Hz, J = 1.7 Hz).
6´ꢀBromoꢀ5ꢀchloroꢀ1,3,3ꢀtrimethylspiro[indolineꢀ2Hꢀpyranoꢀ
2,2´ꢀ[3,2ꢀh]quinoline] (13). The yield was 47%, m.p. 209—210 °С
(from heptane). Found (%): C, 60.00; H, 4.25; N, 6.43.
C22H18BrClN2O. Calculated (%): C, 59.82; H, 4.11; N, 6.34.
1H NMR (CDCl3), δ: 1.18 (s, 3 H, 3ꢀMe); 1.31 (s, 3 H, 3ꢀMe); 2.77
(s, 3 H, 1ꢀMe); 5.76 (d, 1 H, H(3´), J = 10.2 Hz); 6.42 (d, 1 H, H(7),
J = 8.2 Hz); 6.89 (d, 1 H, H(4´), J = 10.2 Hz); 7.00 (d, 1 H, H(4),
J = 2.1 Hz); 7.09 (dd, 1 H, H(6), J = 8.2 Hz, J = 2.1 Hz); 7.39 (dd,
1 H, H(8´), J = 8.6 Hz, J = 4.2 Hz); 7.52 (s, 1 H, H(5´)); 8.36 (dd,
1 H, H(7´), J = 8.6 Hz, J = 1.6 Hz); 8.80 (dd, 1 H, H(9´), J = 4.2 Hz,
J = 1.6 Hz).
5,6´ꢀDichloroꢀ1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ2Hꢀpyraꢀ
no[3,2ꢀh]quinoline] (14). The yield was 55%, m.p. 186—187 °С
(from heptane). Found (%): C, 66.37; H, 4.48; N, 7.16.
C22H18Cl2N2O. Calculated (%): C, 66.51; H, 4.57; N, 7.05.
1H NMR (CDCl3), δ: 1.18 (s, 3 H, 3ꢀMe); 1.31 (s, 3 H, 3ꢀMe); 2.76
(s, 3 H, 1ꢀMe); 5.76 (d, 1 H, H(3´), J = 10.2 Hz); 6.42 (d, 1 H, H(7),
J = 8.2 Hz); 6.88 (d, 1 H, H(4´), J = 10.2 Hz); 7.00 (d, 1 H, H(4),
J = 2.1 Hz); 7.09 (dd, 1 H, H(6), J = 8.2 Hz, J = 2.1 Hz); 7.33 (s,
1 H, H(5´)); 7.39 (dd, 1 H, H(8´), J = 8.6 Hz, J = 4.2 Hz); 8.40 (dd,
1 H, H(7´), J = 8.6 Hz, J = 1.6 Hz); 8.82 (dd, 1 H, H(9´), J = 4.2 Hz,
J = 1.6 Hz).
Synthesis of spiropyrans 15—22 (general procedure).
A solution of Et3N (1 mmol) in butanꢀ2ꢀone (2 mL) was added to a
boiling mixture of the corresponding 3Нꢀindolium halide 7—10
(1 mmol), formylquinolinol 3 or 4 (1.05 mmol), and 2ꢀbutanone
(15 mL) under argon atmosphere for 30 min. The mixture was
refluxed for 16 h and cooled, the solvent was evaporated. The residue
was purified by column chromatography on Аl2O3, eluent was
CHCl3 (compounds 15—18), or on SiO2 with benzene—acetone
(4 : 1) as the eluent (compounds 19 and 20) followed by
recrystallization. In case of compounds 21 and 22, the residue was
triturated with a small amount of acetone, filtered off, washed with
acetone, and recrystallized.
K = kAB/kBA
1/τ = kAB + kBA
.
Thermodynamic parameters of the equilibrium between cyclic
and merocyanine forms were determined from the Vant Hoff equaꢀ
tion:
lnK = –∆H°/RT + ∆S°/R.
Activation energy values of the thermal processes were obtained
from the Arrhenius equation
lnk = –Ea/RT + lnA.
Toluene from Fluka was used for the preparation of solutions.
All the measurements were performed at 20 °С.
Compounds 2 (Fluka), 5 (Lancaster), and 6 (Aldrich) were
used as purchased, compounds 1,24 7,25 8,26 9,27 and 10 (see Ref.
28) were obtained according to procedures described earlier.
Synthesis of formylquinolinols 3 and 4 (general procedure).
A mixture of 5ꢀhaloquinolinol 1 or 2 (15 mmol), hexamethyleneteꢀ
tramine (4.2 g, 30 mmol), and trifluoroacetic acid (25 mL) was
refluxed for 6 h under argon atmosphere, cooled, poured in
a mixture of concentrated НСl (20 mL) and water (220 mL), and
neutralized to рН ~5. A precipitate formed was filtered off, washed
with water, and dried in air. The precipitate was extracted with hot
benzene (3×20 mL), the solvent was evaporated, and the residue was
crystallized from ethanol.
5ꢀBromoꢀ8ꢀhydroxyquinolineꢀ7ꢀcarbaldehyde (3). The yield was
14%, m.p. 209—210 °С. Found (%): C, 47.80; H, 2.49; N, 5.43.
C10H6BrNO2. Calculated (%): C, 47.65; H, 2.40; N, 5.56.
1H NMR, δ: 7.68 (dd, 1 Н, Н(3), J = 4.3 Hz, J = 8.6 Hz); 8.06 (s,
1 Н, Н(6)); 8.51 (dd, 1 Н, Н(4), J = 1.5 Hz, J = 8.6 Hz); 8.93 (dd,
1 Н, Н(2), J = 1.5 Hz, J = 4.3 Hz); 10.38 (s, 1 Н, 7ꢀСНО).
5ꢀChloroꢀ8ꢀhydroxyquinolineꢀ7ꢀcarbaldehyde (4). The yield
was 15%, m.p. 211—212 °С. Found (%): C, 57.97; H, 3.15; N,
6.86. C10H6ClNO2. Calculated (%): C, 57.85; H, 2.91; N, 6.75.
1H NMR, δ: 7.69 (dd, 1 Н, Н(3), J = 4.2 Hz, J = 8.5 Hz); 7.85 (s,
1 Н, Н(6)); 8.54 (dd, 1 Н, Н(4), J = 1.4 Hz, J = 8.5 Hz); 8.92 (dd,
1 Н, Н(2), J = 1.4 Hz, J = 4.2 Hz); 10.37 (s, 1 Н, 7ꢀСНО).
Synthesis of spiropyrans 11—14 (general procedure). A solution
of 2ꢀmethyleneindoline 5 or 6 (1 mmol) in butanꢀ2ꢀone (2 mL)
was added to a boiling solution of formylquinolinol 3 or 4
(1.05 mmol) in 2ꢀbutanone (15 mL) under argon atmosphere for 30
min. The mixture was refluxed for 16 h, the solvent was evaporated,
the residue was purified by column chromatography on Аl2O3
(eluent, CHCl3) and recrystallized.
6´ꢀBromoꢀ1ꢀhexadecyloxyꢀ3,3ꢀdimethylspiro[indolineꢀ
2,2´ꢀ2Hꢀpyrano[3,2ꢀh]quinoline] (15). The yield was 46%, m.p.
87—88 °С (from heptane). Found (%): C, 70.61; H, 8.03; N, 4.48.
C38H51BrN2O2. Calculated (%): C, 70.46; H, 7.94; N, 4.32.
1H NMR (CDCl3), δ, Аꢀform: 0.86 (t, 3 H, 5ꢀOC16H33, J =
6.9 Hz); 1.19 (s, 3 H, 3ꢀMe); 1.22—1.28 (m, 24 H, 5ꢀOC16H33);
1.31 (s, 3 H, 3ꢀMe); 1.44 (m, 2 H, 5ꢀOC16H33); 1.76 (m, 2 H,
6´ꢀBromoꢀ1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ2Hꢀpyraꢀ
no[3,2ꢀh]quinoline] (11). The yield was 67%, m.p. 186—187.5 °С
(from heptane) (cf. Ref. 12: m.p. 195 °C). Found (%): C, 65.05; H,
4.62; N, 7.03. C22H19BrN2O. Calculated (%): C, 64.87; H, 4.70;
N, 6.88. 1H NMR (CDCl3), δ: 1.19 (s, 3 H, С(3)Ме); 1.34 (s, 3 H,
С(3)Ме); 2.79 (s, 3 H, NМе); 5.78 (d, 1 H, Н(3´), J = 10.2 Hz);
6.52 (d, 1 Н, Н(7), J = 7.7 Hz); 6.82 (dt, 1 H, H(5), J = 7.4 Hz,
J = 0.9 Hz); 6.87 (d, 1 H, Н(4´), J = 10.2 Hz); 7.06 (dd, 1 H, H(4),
J = 7.3 Hz, J = 1.1 Hz); 7.15 (dt, 1 H, H(6), J = 7.7 Hz, J = 1.2 Hz);
7.37 (dd, 1 H, H(8´), J = 8.6 Hz, J = 4.2 Hz); 7.52 (s, 1 Н, Н(5´));
5ꢀOC16H33); 2.72 (s, 3 H, 1ꢀMe); 3.90 (t, 2 H, 5ꢀOC16H33
,
J = 6.6 Hz); 5.77 (d, 1 H, H(3´), J = 10.2 Hz); 6.41 (d, 1 H, H(7),
J = 8.2 Hz); 6.67 (dd, 1 H, H(6), J = 8.2 Hz, J = 2.5 Hz); 6.71 (d,
1 H, H(4), J = 2.5 Hz); 6.86 (d, 1 H, H(4´), J = 10.2 Hz); 7.37 (dd,
1 H, H(8´), J = 8.6 Hz, J = 4.2 Hz); 7.51 (s, 1 H, H(5´)); 8.35 (dd,
1 H, H(7´), J = 8.6 Hz, J = 1.7 Hz); 8.76 (dd, 1 H, H(9´), J = 4.2 Hz,

6´ꢀHalospiro[indolinepyranoquinolines]
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
157
J = 1.7 Hz); Вꢀform: 0.86 (t, 3 H, 5ꢀOC16H33, J = 6.9 Hz); 1.22—
1.28 (m, 24 H, 5ꢀOC16H33); 1.44 (m, 2 H, 5ꢀOC16H33); 1.71 (s,
6 H, 3ꢀMe); 1.76 (m, 2 H, 5ꢀOC16H33); 3.53 (s, 3 H, 1ꢀMe); 3.95
(t, 2 H, 5ꢀOC16H33, J = 6.6 Hz); 6.69 (d, 1 H, H(4´), J = 14.0 Hz);
6.83 (dd, 1 H, H(6), J = 8.8 Hz, J = 2.2 Hz); 6.87 (d, 1 H, H(3´),
J = 14.0 Hz); 6.89 (d, 1 H, H(4), J = 2.2 Hz); 6.90 (d, 1 H, H(7),
J = 8.8 Hz); 7.45 (dd, 1 H, H(8´), J = 8.2 Hz, J = 4.4 Hz); 7.51 (s,
1 H, H(5´)); 8.15 (dd, 1 H, H(7´), J = 8.2 Hz, J = 1.5 Hz); 8.74 (dd,
1 H, H(9´), J = 4.4 Hz, J = 1.5 Hz).
6´ꢀChloroꢀ1ꢀhexadecyloxyꢀ3,3ꢀdimethylspiro[indolineꢀ
2,2´ꢀ2Нꢀpyrano[3,2ꢀh]quinoline] (16). The yield was 53%, m.p.
74—75 °С (from hexane). Found (%): C, 75.76; H, 8.63; N, 4.70.
C38H51ClN2O2. Calculated (%): C, 75.66; H, 8.52; N, 4.64.
1H NMR (CDCl3), δ, Аꢀform: 0.88 (t, 3 H, 5ꢀOC16H33, J =
6.9 Hz); 1.21 (s, 3 H, 3ꢀMe); 1.22—1.31 (m, 24 H, 5ꢀOC16H33);
1.33 (s, 3 H, 3ꢀMe); 1.47 (m, 2 H, 5ꢀOC16H33); 1.76 (m, 2 H, 5ꢀ
OC16H33); 2.74 (s, 3 H, 1ꢀMe); 3.91 (t, 2 H, 5ꢀOC16H33, J =
6.6 Hz); 5.80 (d, 1 H, H(3´), J = 10.2 Hz); 6.43 (d, 1 H, H(7), J =
8.2 Hz); 6.70 (dd, 1 H, H(6), J = 8.2 Hz, J = 2.5 Hz); 6.73 (d, 1 H,
H(4), J = 2.5 Hz); 6.88 (d, 1 H, H(4´), J = 10.2 Hz); 7.34 (s, 1 H,
H(5´)); 7.40 (dd, 1 H, H(8´), J = 8.5 Hz, J = 4.2 Hz); 8.41 (dd, 1 H,
H(7´), J = 8.6 Hz, J = 1.7 Hz); 8.82 (dd, 1 H, H(9´), J = 4.2 Hz,
J = 1.7 Hz); Вꢀform: 0.88 (t, 3 H, 5ꢀOC16H33, J = 6.9 Hz); 1.22—
1.31 (m, 24 H, 5ꢀOC16H33); 1.47 (m, 2 H, 5ꢀOC16H33); 1.73 (s,
6 H, 3ꢀMe); 1.76 (m, 2 H, 5ꢀOC16H33); 3.55 (s, 3 H, 1ꢀMe); 3.97
(t, 2 H, 5ꢀOC16H33, J = 6.6 Hz); 6.70 (d, 1 H, H(4´), J = 14.0 Hz);
6.85 (dd, 1 H, H(6), J = 8.8 Hz, J = 2.2 Hz); 6.89 (d, 1 H, H(3´),
J = 14.0 Hz); 6.91 (d, 1 H, H(4), J = 2.2 Hz); 6.92 (d, 1 H, H(7),
J = 8.8 Hz); 7.34 (s, 1 H, H(5´)); 7.49 (dd, 1 H, H(8´), J = 8.2 Hz,
J = 4.4 Hz); 8.21 (dd, 1 H, H(7´), J = 8.2 Hz, J = 1.5 Hz); 8.79 (dd,
1 H, H(9´), J = 4.4 Hz, J = 1.5 Hz).
1ꢀBenzylꢀ6´ꢀbromoꢀ3,3ꢀdimethylspiro[indolineꢀ2,2´ꢀ2Нꢀ
pyrano[3,2ꢀh]quinoline] (17). The yield was 48%, m.p. 176—177
°С (from heptane). Found (%): C, 69.50; H, 4.95; N, 5.91.
C28H23BrN2O. Calculated (%): C, 69.57; H, 4.80; N, 5.79. 1H
NMR (CDCl3), δ: 1.30 (s, 3 H, С(3)Ме); 1.38 (s, 3 H, С(3)Ме);
4.36 (d, 1 H, 1ꢀCH2Ph, J = 16.8 Hz); 4.63 (d, 1 H, 1ꢀCH2Ph,
J = 16.8 Hz); 5.84 (d, 1 H, H(3´), J = 10.2 Hz); 6.30 (d, 1 H, H(7),
J = 7.7 Hz); 6.82 (d, 1 H, H(4´), J = 10.2 Hz); 6.83 (dt, 1 H, H(5),
J = 7.4 Hz, J = 0.9 Hz); 7.02 (dt, 1 H, H(6), J = 7.7 Hz, J = 1.2 Hz);
7.10 (dd, 1 H, H(4), J = 7.3 Hz, J = 1.1 Hz); 7.17—7.29 (m, 5 H,
1ꢀCH2Ph); 7.39 (dd, 1 H, H(8´), J = 8.6 Hz, J = 4.2 Hz); 7.49 (s,
1 H, H(5´)); 8.36 (dd, 1 H, H(7´), J = 8.6 Hz, J = 1.6 Hz); 8.80 (dd,
1 H, H(9´), J = 4.2 Hz, J = 1.6 Hz).
1ꢀBenzylꢀ6´ꢀchloroꢀ3,3ꢀdimethylspiro[indolineꢀ2,2´ꢀ2Нꢀ
pyrano[3,2ꢀh]quinoline] (18). The yield was 51%, m.p. 156—
157 °С (from heptane). Found (%): C, 76.72; H, 5.43; N, 6.29.
C28H23ClN2O. Calculated (%): C, 76.62; H, 5.28; N, 6.38.
1H NMR (CDCl3), δ: 1.30 (s, 3 H, С(3)Ме); 1.38 (s, 3 H, С(3)Ме);
4.35 (d, 1 H, 1ꢀCH2Ph, J = 16.8 Hz); 4.62 (d, 1 H, 1ꢀCH2Ph,
J = 16.8 Hz); 5.85 (d, 1 H, H(3´), J = 10.2 Hz); 6.30 (d, 1 H, Н(7),
J = 7.7 Hz); 6.82 (d, 1 H, Н(4´), J = 10.2 Hz); 6.82 (dt, 1 H, Н(5),
J = 7.4 Hz, J = 0.9 Hz); 7.02 (dt, 1 H, Н(6), J = 7.7 Hz, J = 1.2 Hz);
7.10 (dd, 1 H, Н(4), J = 7.3 Hz, J = 1.0 Hz); 7.17—7.29 (m, 5 H,
1ꢀCH2Ph); 7.30 (s, 1 H, Н(5´)); 7.39 (dd, 1 H, Н(8´), J = 8.6 Hz,
J = 4.2 Hz); 8.40 (dd, 1 H, Н(7´), J = 8.6 Hz, J = 1.6 Hz); 8.81 (dd,
1 H, Н(9´), J = 4.2 Hz, J = 1.6 Hz).
N, 6.41. 1H NMR (CDCl3), δ, Аꢀform: 1.20 (s, 3 H, 3ꢀMe); 1.34 (s,
3 H, 3ꢀMe); 1.75 (s, 1 H, OH); 3.49—3.87 (m, 4 H,
1ꢀCH2CH2OH); 5.77 (d, 1 H, H(3´) J = 10.2 Hz); 6.67 (d, 1 H,
H(7), J = 7.9 Hz); 6.88 (d, 1 H, H(4´), J = 10.2 Hz); 6.96 (dt, 1 H,
H(5), J = 7.4 Hz, J = 0.9 Hz); 7.08 (dd, 1 H, H(4), J = 7.3 Hz,
J = 1.0 Hz); 7.17 (dt, 1 H, H(6), J = 7.7 Hz, J = 1.2 Hz); 7.41 (dd,
1 H, H(8´), J = 8.5 Hz, J = 4.2 Hz); 7.54 (s, 1 H, H(5´)); 8.37 (dd,
1 H, H(7´), J = 8.5 Hz, J = 1.6 Hz), 8.76 (dd, 1 H, H(9´), J = 4.2 Hz,
J = 1.6 Hz); Сꢀform: 1.22 (s, 3 H, 3ꢀMe); 1.49 (s, 3 H, 3ꢀMe);
3.49—3.87 (m, 4 H, 1ꢀCH2CH2OH); 6.52 (d, 1 H, H(3´),
J = 16.1 Hz); 6.83 (d, 1 H, H(7), J = 7.8 Hz); 6.96 (dt, 1 H, H(5),
J = 7.4 Hz, J = 0.9 Hz); 7.10 (dd, 1 H, H(4), J = 7.4 Hz, J = 1.0 Hz);
7.18 (dt, 1 H, H(6), J = 7.7 Hz, J = 1.3 Hz); 7.30 (d, 1 H, H(4´),
J = 16.1 Hz); 7.52 (dd, 1 H, H(8´), J = 8.5 Hz, J = 4.3 Hz); 7.93 (s,
1 H, H(5´)); 8.43 (dd, 1 H, H(7´), J = 8.5 Hz, J = 1.5 Hz); 8.64 (s,
1 H, OH); 8.79 (dd, 1 H, H(9´), J = 4.3 Hz, J = 1.5 Hz).
6´ꢀChloroꢀ1ꢀ(2ꢀhydroxyethyl)ꢀ3,3ꢀdimethylspiro[indolineꢀ
2,2´ꢀ2Нꢀpyrano[3,2ꢀh]quinoline] (20). The yield was 57%, m.p.
159—160.5 °С (from heptane—toluene, 2.5 : 1). Found (%): C,
70.49; H, 5.50; N, 6.99. C23H21ClN2O2. Calculated (%): C, 70.31;
H, 5.39; N, 7.13. 1H NMR (CDCl3), δ, Аꢀform: 1.18 (s, 3 H,
3ꢀMe); 1.33 (s, 3 H, 3ꢀMe); 1.73 (s, 1 H, 1ꢀCH2CH2OH);
3.40—3.88 (m, 4 H, 1ꢀCH2CH2OH); 5.75 (d, 1 H, H(3´),
J = 10.2 Hz); 6.64 (d, 1 H, H(7), J = 7.8 Hz); 6.86 (d, 1 H, H(4´),
J = 10.2 Hz); 6.94 (dt, 1 H, H(5), J = 7.4 Hz, J = 0.9 Hz); 7.06 (dd,
1 H, H(4), J = 7.3 Hz, J = 0.9 Hz); 7.15 (dt, 1 H, H(6), J = 7.7 Hz,
J = 1.2 Hz); 7.33 (s, 1 H, H(5´)); 7.39 (dd, 1 H, H(8´), J = 8.6 Hz,
J = 4.2 Hz); 8.39 (dd, 1 H, H(7´), J = 8.6 Hz, J = 1.7 Hz); 8.78 (dd,
1 H, H(9´), J = 4.2 Hz, J = 1.6 Hz); Сꢀform: 1.20 (s, 3 H, 3ꢀMe);
1.47 (s, 3 H, 3ꢀMe); 3.40—3.88 (m, 4 H, 1ꢀCH2CH2OH); 6.50 (d,
1 H, H(3´), J = 16.1 Hz); 6.81 (d, 1 H, H(7), J = 7.9 Hz); 6.94 (dt,
1 H, H(5), J = 7.4 Hz, J = 0.9 Hz); 7.08 (dd, 1 H, H(4), J = 7.3 Hz,
J = 0.9 Hz); 7.16 (dt, 1 H, H(6), J = 7.7 Hz, J = 1.2 Hz); 7.30 (d,
1 H, H(4´), J = 16.1 Hz); 7.51 (dd, 1 H, H(8´), J = 8.5 Hz,
J = 4.3 Hz); 7.72 (s, 1 H, H(5´)); 8.46 (dd, 1 H, H(7´), J = 8.5 Hz,
J = 1.5 Hz); 8.57 (s, 1 H, OH); 8.79 (dd, 1 H, H(9´), J = 4.3 Hz,
J = 1.5 Hz).
6´ꢀBromoꢀ1ꢀ(2ꢀcarboxyethyl)ꢀ3,3ꢀdimethylspiro[indolineꢀ
2,2´ꢀ2Нꢀ[3,2ꢀh]quinoline] (21). The yield was 50%, m.p. 206—
207 °С (from diethyl ketone). Found (%): C, 62.10; H, 4.45;
N, 6.11. C24H21BrN2O3. Calculated (%): C, 61.95; H, 4.55;
N, 6.02. 1H NMR (DMSOꢀd6), δ: 1.06 (s, 3 H, 3ꢀMe); 1.17 (s, 3 H,
3ꢀMe); 2.49 (m, 2 H, 1ꢀCH2CH2COOH); 4.39 (m, 2 H,
1ꢀCH2CH2COOH); 5.91 (d, 1 H, H(3´), J = 10.2 Hz); 6.64 (d, 1 H,
H(7), J = 7.7 Hz); 6.79 (dt, 1 H, H(5), 5ꢀH, J = 7.3 Hz, J = 0.9 Hz);
7.09 (dd, 1 H, H(4), J = 7.3 Hz, J = 0.9 Hz); 7.12 (dt, 1 H, H(6),
6ꢀH, J = 7.6 Hz, J = 1.2 Hz); 7.13 (d, 1 H, H(4´), J = 10.2 Hz); 7.57
(dd, 1 H, H(8´), J = 8.6 Hz, J = 4.2 Hz); 7.84 (s,1 H, H(5´)); 8.33
(dd, 1 H, H(7´), J = 8.6 Hz, J = 1.5 Hz); 8.75 (dd, 1 H, H(9´),
J = 4.2 Hz, J = 1.5 Hz).
1ꢀ(2ꢀCarboxyethyl)ꢀ6´ꢀchloroꢀ3,3ꢀdimethylspiro[indolineꢀ
2,2´ꢀ2Нꢀpyrano[3,2ꢀh]quinoline] (22). The yield was 54%, m.p.
203—204 °С (from diethyl ketone). Found (%): C, 68.65; H, 4.92;
N, 6.73. C24H21ClN2O3. Calculated (%): C, 68.49; H, 5.03; N,
6.66. 1H NMR (DMSOꢀd6), δ: 1.09 (s, 3 H, 3ꢀMe); 1.19 (s, 3 H,
3ꢀMe); 2.50 (m, 2 H, 1ꢀCH2CH2COOH); 4.42 (m, 2 H,
1ꢀCH2CH2COOH); 5.94 (d, 1 H, H(3´), J = 10.2 Hz); 6.66 (d, 1 H,
H(7), J = 7.7 Hz); 6.81 (dt, 1 H, H(5), J = 7.3 Hz, J = 0.9 Hz); 7.12
(dd, 1 H, H(4), J = 7.3 Hz, J = 0.9 Hz); 7.14 (dt, 1 H, H(6), J =
7.6 Hz, J = 1.2 Hz); 7.15 (d, 1 H, H(4´), J = 10.2 Hz); 7.60 (dd, 1 H,
H(8´), J = 8.6 Hz, J = 4.2 Hz); 7.69 (s, 1 H, H(5´)); 8.41 (dd, 1 H,
6´ꢀBromoꢀ1ꢀ(2ꢀhydroxyethyl)ꢀ3,3ꢀdimethylspiro[indolineꢀ
2,2´ꢀ2Нꢀ[3,2ꢀh]quinoline] (19). The yield was 52%, m.p. 171—
172 °С (from heptane—toluene, 2.5 : 1). Found (%): C, 63.35; H,
4.67; N, 6.52. C23H21BrN2O2. Calculated (%): C, 63.17; H, 4.84;

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
Voloshin et al.
H(7´), J = 8.6 Hz, J = 1.6 Hz); 8.80 (dd, 1 H, H(9´), J = 4.2 Hz,
J = 1.6 Hz).
13. J. D. Winkler, C. M. Bowen, V. Michelet, J. Am. Chem. Soc.,
1998, 120, 3237.
14. L. Evans, G. E. Collins, R. E. Shaffer, V. Michelet, J. D.
This work was financially supported by the Russian
Federation President Council for Grants (Program for
the State Support of Leading Scientific Schools of the
RF, Grant NShꢀ4849.2006.3), by the Russian Foundaꢀ
tion for Basic Research (Projects No. 06ꢀ03ꢀ32988ꢀа
and No. 05ꢀ03ꢀ08087ꢀofi_a), and by the Ministry of
Education and Science of the RF (Department Scientific
Program “Development of Scientific Potential of the
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