Synthesis of photoactive bichromophoric dyads containing 2-styrylquinoline and 2-naphthol moieties

Article abstract of DOI:10.1007/s11172-011-0222-8

A three-step approach to the synthesis of bichromophoric dyads of the general formula SQ - (CH₂)_n - Np (SQ is the 2-(4-oxystyryl)quinoline moiety, Np is the 3-oxy-2-naphthol moiety, n = 2, 4, 5) was developed from available reagents.

Full text of DOI:10.1007/s11172-011-0222-8

Russian Chemical Bulletin, International Edition, Vol. 60, No. 7, pp. 1495—1499, July, 2011
1495
Synthesis of photoactive bichromophoric dyads containing
2ꢀstyrylquinoline and 2ꢀnaphthol moieties
T. N. Gavrishova,a V. M. Li,a K. F. Sadykova,a,b and M. F. Budykaa
aInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (496) 514 3244. Eꢀmail: tngavr@icp.ac.ru
bBashkir State University, Department of Chemistry,
32 ul. Z. Validi, 450074 Ufa, Russian Federation
A threeꢀstep approach to the synthesis of bichromophoric dyads of the general formula
SQ—(CH2)n—Np (SQ is the 2ꢀ(4ꢀoxystyryl)quinoline moiety, Np is the 3ꢀoxyꢀ2ꢀnaphthol
moiety, n = 2, 4, 5) was developed from available reagents.
Key words: styrylquinoline, condensation, microwave irradiation, alkylation, bichromoꢀ
phoric dyads.
Nowadays, a large amount of works are devoted to the
studies of principles of construction and functioning of
molecular logical gates (MLG),1—6 i.e., molecular sysꢀ
tems, which are transformed from one stable state to anꢀ
other upon an external action (the input signal). The propꢀ
erties of the initial and final states determine the type of an
output signal, whereas the input/output signal proportion
is determined by the table of the truth of logical function.
We have shown7,8 that 2ꢀstyrylquinoline (2SQ) derivꢀ
atives can be used in the construction of different MLG,
which are able to function both in solutions and polymeric
matrices. Exposure to light and addition of an acid are the
input signals for such MLG, whereas optical density on a
certain wavelength is the output signal.
To sum up, a photon MLG is a molecular photoswitch
capable to exist in several states, whose interconversions
can be accomplished upon the action of light. In order to
simulate the functioning of such switches, we synthesized
bichromophoric dyads containing the 2SQ and 2Np moiꢀ
eties, which are bound with an oxypolymethylene "bridge"
(Scheme 1).
Results and Discussion
There are several approaches to the synthesis of bichroꢀ
mophoric dyads containing fragments of 2SQ and 2Np
from available reagents (quinaldine, 4ꢀhydroxybenzaldeꢀ
hyde, 2,3ꢀdihydroxynaphthalene, and dibromoalkane) (see
Scheme 1).
To return the 2SQꢀderived MLG to the initial state
(reversibility is a necessary condition for the MLG funcꢀ
tioning), an acid should be neutralized, for example, by
addition of an alkali. However, the use of extra reagents
(acids, alkalis) sets limits on the applicability of MLG.
The optimum are completely photon MLG,9 in which
both the isomerization and protonation reactions proceed
upon the action of light. Photoacids, for example naphꢀ
thols, can be used for the latter reaction. The compound
2SQ has an acidity constant pKa = 4.8.10 For 2ꢀnaphthol
(2Np) the acidity constants in the ground and the lowest
singlet excited states are equal to 9.5 and 2.8, respectively.11
Therefore, the ground (S0) state of the 2SQ—2Np system
has the proton on the hydroxy oxygen atom, and there are
thermodynamic prerequisites for the proton to be photoꢀ
transferred upon excitation of 2Np. In this case, instead of
addition of an acid one can use exposure to the light from
the region of absorption of 2Np, that can lead to the forꢀ
mation of the protonated form of 2SQ.
Method A suggests a condensation of 4ꢀhydroxybenzꢀ
aldehyde with quinaldine in the first step to form 2ꢀ(4ꢀhydrꢀ
oxystyryl)quinoline (1), which is further alkylated with
dibromoalkane to the corresponding bromoalkoxystyrylꢀ
quinoline 2. Compound 2 can be also obtained by method
B, which includes an initial preparation of bromoalkoxyꢀ
benzaldehyde 3, followed by the condensation reaction.
We studied this possibility using alkylation of 4ꢀhyꢀ
droxybenzaldehyde with 1,2ꢀdibromoethane and 1,4ꢀdiꢀ
bromobutane as examples. The reactions were carried out
under various conditions described in the literature: in the
alcoholic alkali12 or in DMF in the presence of potassium
carbonate.13 In both cases, the mixtures of monoꢀ and
dialkylated products were obtained and the yields of the
target bromoalkoxybenzaldehyde 3 did not exceed 45%.
To increase the yield of monoalkylated product, we used
a dibromoalkane excess, however, the latter complicated isoꢀ
lation of the target product from the reaction mixture.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1470—1474, July, 2011.
1066ꢀ5285/11/6007ꢀ1495 © 2011 Springer Science+Business Media, Inc.

1496
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 7, July, 2011
Gavrishova et al.
Scheme 1
n = 2 (a), 4 (b), 5 (c)
The aldehydes 3a and 3b obtained were further used in
the condensation with quinaldine for the synthesis of the
corresponding styrylquinolines 2a and 2b. The reaction
was carried out in acetic anhydride, the reaction mixture
was heated for 14 h. The total twoꢀstep yield of styrylquinoꢀ
lines was <24% and required laborious purification by
column chromatography, large amounts of reagents and
solvents. We did not try method C (the reaction of 3 with
dihydroxynaphthalene) because of the low yields of bromoꢀ
alkoxybenzaldehydes 3 and their complicated isolation.
We did not consider another synthesis either, which uses
an alkylation of dihydroxynaphthalene with dibromoꢀ
alkane in the first step, since in this case both reactants
have two equivalent functional groups, that can lead to the
formation of several byꢀproducts (oligomers and cyclic
structures).
Method A proved to be the most efficient, whose first
step includes the condensation of quinaldine with 4ꢀhydrꢀ
oxybenzaldehyde. This condensation can be accomplished
by different ways. It is commonly carried out in the presꢀ
ence of acetic anhydride.14 The disadvantages of this way
are a prolonged heating and the use of acetic anhydride as
a solvent and a catalyst, which reacts with the hydroxy
group to form 2ꢀ(4ꢀacetoxystyryl)quinoline, which should
be hydrolyzed to the target hydroxy derivative 1. The reacꢀ
tion virtually proceeds in two steps and requires purificaꢀ
tion of 2ꢀ(4ꢀacetoxystyryl)quinoline obtained in the first
step on a column with silica gel with its subsequent recrysꢀ
tallization. We have suggested a convenient oneꢀstep solꢀ
ventꢀ and catalystꢀfree approach to the synthesis of
4ꢀhydroxystyrylquinolines upon the action of microwave
irradiation.15 The condensation in this case is completed
within 9—12 min. Hydroxystyrylquinoline 1 can be easily
isolated by simple workꢀup of the reaction mixture with
aqueous alcohol, with the yield being as high as 90%.
Further, we carried out alkylation of compound 1 with
different dibromoalkanes: 1,2ꢀdibromoethane, 1,4ꢀdibroꢀ
mobutane, and 1,5ꢀdibromopentane. The phenoxide anꢀ
ion was generated using potassium carbonate, whereas
2ꢀbutanone was a solvent, since in acetone the reaction
was too slow. We used a tenfold excess of dibromoalkane
to suppress the dialkylation reaction. The ability of the
starting compound 1 to form a water soluble sodium salt
was used for the separation of the product from it. Comꢀ
pounds 2a—c were converted to hydro chlorides for the
products to be separated from excess dibromoalkane, since,
unlike dibromoalkanes, they are insoluble in hexane. Thus,
bromoalkoxystyrylquinolines 2a—c were synthesized in
62—91% yields.
The thus obtained bromoalkoxystyrylquinolines 2 were
further involved into the reaction with 2,3ꢀdihydroxyꢀ
naphthalene. The naphthoxide anion was also generated

Supramolecular styrylquinolineꢀnaphthol dyads
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 7, July, 2011
1497
E•10–4/L mol–1 cm–1
using potassium carbonate, the reaction was carried out in
2ꢀbutanone, since in acetone it was very slow because of
its low boiling point. We used excess of 2,3ꢀdihydrꢀ
oxynaphthalene to suppress alkylation of the second hydrꢀ
oxy group. This method furnished the target compounds
4a—c in 42—85% yields.
4
8
6
When the two methods for the construction of dyads
4a,b containing a quinoline and a naphthalene moieties
are compared, it becomes obvious that the synthesis based
on the use of hydroxystyrylquinoline 1 as the intermediate
(way A) is more efficient than the alternative approach
(way B), when 4ꢀhydroxybenzaldehyde is alkylated in the
first step (Table 1).
4
2
3
2
1
The structures of compounds 2a—c and 4a—c were
250
300
350
400
λ/nm
1
confirmed by the H NMR, IR, and UVꢀvisible spectroꢀ
Fig. 1. Absorption spectra (in ethanol) of 3ꢀmethoxynaphthꢀ2ꢀ
ol (1), 2ꢀ(4ꢀethoxystyryl)quinoline (2), and compound 4b (3), as
well as the sum of the first two spectra (4).
1
scopic data. The H NMR spectra of these compounds
exhibit signals for the olefin protons of the styryl fragment
in the region δ 7—8 as doublets with the vicinal spinꢀspin
coupling constants 16—17 Hz, that indicates the transꢀ
arrangement of the double bond. The presence of the band
of outꢀofꢀplane bending vibrations of the C—H bonds at
the C=C double bond in the region 968—982 cm–1 of the
IR spectra confirms the transꢀarrangement of the double
bond. In addition, the IR spectra of compounds 2a—c
exhibit a characteristic band of stretching vibrations of the
C—Br bond in the region 510—515 cm–1, whereas a broad
band characteristic of the OH group is observed for comꢀ
photoisomerization, that creates prerequisites for the simꢀ
ulation of functioning of controlled molecular photoꢀ
switches on their basis. Measurement of quantum yields of
the reaction, their dependence from the length of the
bridged group in the supramolecular system and from the
pH of the medium, as well as determination of the type of
logical operations, which can be accomplished by comꢀ
pounds 4a—c, are subjects of our further studies.
In conclusion, starting from available reagents we deꢀ
veloped an efficient threeꢀstep synthesis of bichromophoric
dyads 4a—c containing styrylquinoline and naphthol moiꢀ
eties, which are bound with oxypolymethylene bridge.
These compounds are promising models for the studies of
principles of functioning of photocontrolled molecular
switches and logical gates.
pounds 4a—c in the region 2400—3600 cm–1
.
The UV spectra of compounds 4a—c virtually are the
sum of the spectra of model compounds, 2ꢀ(4ꢀethoxyꢀ
styryl)quinoline and 3ꢀmethoxynaphtholꢀ2, as it is shown
in Fig. 1 for compound 4b taken as an example. Compariꢀ
son with the spectra of model compounds shows that an
absorption band in the region 230 nm is basically related
to the absorption of naphthol, whereas styrylquinoline abꢀ
sorbs exclusively in the region of wavelengths higher
350 nm, that creates the prerequisites for the selective
excitation of different chromophoric groups depending on
the wavelength of the acting light.
Experimental
1
H NMR spectra were recorded on a Bruker Avance III
spectrometer (500 MHz) in CDCl3 and DMSOꢀd6, Me4Si was
used as an internal standard. IR spectra were recorded on
a Spectrum BXꢀ2 Fourierꢀspectrometer in KBr pellets. Electron
absorption spectra were recorded on a Specord Mꢀ400 spectroꢀ
photometer.
Preliminary studies of photochemical activity of comꢀ
pounds 4a—c showed that their exposure to the UV light
produces spectral changes characteristic of the trans—cisꢀ
Melting points were measured on a Kofler heating stage at
the rate of heating 4 °C min–1. TLC analysis was performed on
ALUGRAM SIL G/UV254 plates, which were visualized under
the UV light. Commercially available (Aldrich) 1,3ꢀdibromoꢀ
ethane, 1,4ꢀdibromobutane, 1,5ꢀdibromopentane, 4ꢀhydroxyꢀ
benzaldehyde, quinaldine, and 2,3ꢀdihydroxynaphthalene were
used as purchased. 2ꢀButanone was distilled before use, potassiꢀ
um carbonate was calcined.
2ꢀ(E)ꢀ(4ꢀHydroxystyryl)quinoline (1). A glass testꢀtube conꢀ
taining quinaldine (0.29 g, 2 mmol) and 4ꢀhydroxybenzaldehyde
(0.49 g, 4 mmol) was placed in a glass with water and irradiated
with microwaves in a consumer oven (600 W) 3 times for 3 min
with 30 s intervals (the total time of irradiation was 9 min). The
reaction progress was controlled by TLC (eluent: acetone—hexꢀ
Table 1. Comparison of different methods for the
synthesis of compounds 4a,b
Method
Total yield
(%)
Comꢀ
pound
Yield
(%)
A
26—77
1
90
2a,b
4a,b
3a,b
2a,b
4a,b
62—91
42—85
37—44
51—52
42—85
B
<20

1498
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 7, July, 2011
Gavrishova et al.
ane (1 : 1)). To isolate compound 1, the reaction mixture was
workedꢀup with aqueous ethanol, the undissolved precipitate
was filtered off, washed with hot ethanol (3×5 mL), dried in
a drying oven. Compound 1 (0.44 g, 90%) was obtained as light
yellow crystals, m.p. 268 °C (from 2ꢀpropanol) (cf. Ref. 14: m.p.
268—270 °C). 1H NMR (CDCl3), δ: 6.76 (d, 2 H, oꢀC6H4O,
J = 8.4 Hz); 7.18 (d, 1 H, =CH—, J = 16.2 Hz); 7.47—7.55
(m, 3 H, mꢀC6H4O, quinoline); 7.66—7.72 (m, 2 H, —CH=,
quinoline); 7.78 (d, 1 H, quinoline, J = 8.6 Hz); 7.88 (d, 1 H,
quinoline, J = 8.0 Hz); 7.92 (d, 1 H, quinoline, J = 8.4 Hz);
8.26 (d, 1 H, quinoline, J = 8.6 Hz); 10.25 (br.s, 1 H, OH). IR,
ν/cm–1: 1636 (νC=C), 968 (outꢀofꢀplane. δ transꢀHC=C—H),
2430—3090 (OH).
4ꢀ(2ꢀBromoethoxy)benzaldehyde (3a). Aqueous 12 M NaOH
(2.1 mL) was added dropwise to a stirred solution of 4ꢀhydroxyꢀ
benzaldehyde (3.05 g, 25 mmol) in 95% ethanol (45 mL) at
~20 °C, the mixture was refluxed for 30 min, followed by addiꢀ
tion of 1,2ꢀdibromoethane (9.4 g, 50 mmol). The reaction mixꢀ
ture that obtained was refluxed for another 4.5 h. After the solꢀ
vent was evaporated on a rotary evaporator, the residue was
diluted by small amounts of water and diethyl ether, which was
accompanied by precipitation of bisꢀ4ꢀformylphenoxyethane, the
latter was filtered off. The ethereal layer was washed with 10%
aq. KOH and water and dried with sodium sulfate. After the
solvent was evaporated, 50% aq. ethanol was added to the resiꢀ
due, and a precipitate of the target product was separated. Comꢀ
pound 3a (2.10 g, 37%) was obtained as white crystals, m.p.
53—55 °C (cf. Ref. 16: m.p. 55—58 °C).
4ꢀ(4ꢀBromobutoxy)benzaldehyde (3b). Potassium carbonate
(10 g, 72 mmol) was added to a solution of 4ꢀhydroxybenzaldeꢀ
hyde (4.88 g, 40 mmol) in anhydrous DMF (40 mL), the mixture
was refluxed for 30 min, followed by addition of 1,4ꢀdibromoꢀ
butane (17.3 g, 80 mmol) and the mixture that obtained was
refluxed for 15 h with stirring. The reaction progress was moniꢀ
tored by TLC (acetone—hexane (1 : 5)). After cooling, the reacꢀ
tion mixture was treated with water and extracted with benzene
(3×100 mL), the solvent was evaporated on a rotary evaporator,
hexane was added to the residue. The hexane extract was sepaꢀ
rated from the oil using a separatory funnel and purified by
column chromatography on Silpearl (eluent: hexane—chloroꢀ
form (1 : 1)). Compound 3b (4.48 g, 44%) was obtained as white
crystals, m.p. 42—44 °C (cf. Ref. 17: m.p. 43 °C).
Synthesis of 2ꢀ[4ꢀ(pꢀbromoalkoxy)styryl]quinolines 2a,b
(method B, general procedure). The corresponding 4ꢀ(pꢀbromoꢀ
alkoxy)benzaldehyde 3 (2 mmol) and acetic anhydride (5 mL)
were added to quinaldine (1 mmol). The reaction mixture was
refluxed for 14 h, cooled, treated with aq. NaHCO3, then exꢀ
tracted with diethyl ether (2×25 mL), and passed through a thin
layer of silica gel. Diethyl ether was evaporated on a rotary evapꢀ
orator, the residue was recrystallized from hexane.
3035, 2930, 2869 (CH2), 1636 (C=C), 1597, 1513, 1248 (COC),
1231, 1185, 959 (—CH=CH), 826, 756, 510 (CBr).
2ꢀ(E)ꢀ[4ꢀ(4ꢀBromobutoxy)styryl]quinoline (2b). The yield
was 0.20 g (52%), white crystals after recrystallization from hexꢀ
ane, m.p. 92—93 °C. Found (%): C, 65.62; H, 5.23; N, 3.47.
C21H20BrNO. Calculated (%): C, 65.98; H, 5.27; N, 3.66.
1H NMR (CDCl3), δ: 1.94—2.01 (m, 2 H, CH2); 2.05—2.13
(m, 2 H, CH2); 3.51 (t, 2 H, CH2Br, J = 6.6 Hz); 4.04 (t, 2 H,
CH2O, J = 6.0 Hz); 6.92 (d, 2 H, oꢀC6H4O, J = 8.6 Hz); 7.28
(d, 1 H, =CH—, J = 16.4 Hz); 7.48 (t, 1 H, quinoline, J = 7.6 Hz);
7.57 (d, 2 H, mꢀC6H4O, J = 8.6 Hz); 7.60—7.66 (m, 2 H, quinoꢀ
line, —CH=); 7.69 (t, 1 H, quinoline, J = 7.6 Hz); 7.77 (d, 1 H,
quinoline, J = 8.0 Hz); 8.06 (d, 1 H, quinoline, J = 8.4 Hz); 8.10
(d, 1 H, quinoline, J = 8.6 Hz). IR, ν/cm–1: 3033, 2953, 2871
(CH2), 1633 (C=C), 1598, 1515, 1249 (COC), 1231, 1184, 958
(—CH=CH), 826, 757, 511 (CBr).
Synthesis of 2ꢀ[4ꢀ(pꢀbromoalkoxy)styryl]quinolines 2a—c
(method A, general procedure). Potassium carbonate (0.41 g,
3 mmol) was added to compound 1 (0.25 g, 1 mmol) in 2ꢀbuꢀ
tanone (10 mL). The reaction mixture was refluxed for 30 min
with magnetic stirring, then a dibromoalkane (n = 2, 4, 5)
(10 mmol) was added, followed by reflux for another 6—24 h
until compound 1 disappeared. The reaction progress was moniꢀ
tored by TLC (acetone—hexane (1 : 5)). After the reaction was
completed, the reaction mixture turned the color from yellow to
white. Aqueous alkali was added to the reaction mixture, the
organic layer was separated and diluted with hydrochloric acid.
The orange precipitate thus formed was filtered off, washed with
hexane (5×3 mL), and dried. Then, acetone (5 mL) and saturatꢀ
ed aq. NaHCO3 (for neutralization) were added to the precipitate,
the mixture was stirred for ~30 min. A white precipitate that formed
was filtered off, dried in air and recrystallized from hexane.
2ꢀ(E)ꢀ[4ꢀ(2ꢀBromoethoxy)styryl]quinoline (2a). The yield
was 0.22 g (62%), white crystals after recrystallization from hexꢀ
ane, m.p. 135—136 °C.
2ꢀ(E)ꢀ[4ꢀ(4ꢀBromobutoxy)styryl]quinoline (2b). The yield
was 0.35 g (91%), white crystals after recrystallization from hexꢀ
ane, m.p. 92—93 °C.
2ꢀ(E)ꢀ[4ꢀ(5ꢀBromopentoxy)styryl]quinoline (2c). The yield
was 0.34 g (85%), white crystals after recrystallization from hexꢀ
ane, m.p. 88—89 °C. Found (%): C, 66.40; H, 5.69; N, 3.44.
C22H22BrNO. Calculated (%): C, 66.67; H, 5.60; N, 3.53.
1H NMR (CDCl3), δ: 1.64—1.71 (m, 2 H, CH2); 1.82—1.90
(m, 2 H, CH2); 1.94—2.02 (m, 2 H, CH2); 3.48 (t, 2 H, CH2Br,
J = 6.8 Hz); 4.04 (t, 2 H, CH2O, J = 6.3 Hz); 6.94 (d, 2 H,
oꢀC6H4O, J = 8.7 Hz); 7.33 (d, 1 H, =CH—, J = 16.2 Hz); 7.51
(t, 1 H, quinoline, J = 7.4 Hz); 7.60 (d, 2 H, mꢀC6H4O, J = 8.7 Hz);
7.64—7.70 (m, 2 H, quinoline, —CH=); 7.72 (t, 1 H, quinoline,
J = 7.7 Hz); 7.79 (d, 1 H, quinoline, J = 7.8 Hz); 8.08—8.16
(m, 2 H, quinoline). IR, ν/cm–1: 3038, 2945, 2867 (CH2), 1637
(C=C), 1592, 1513, 1254 (COC), 1174, 972 (—CH=CH), 835,
752, 515 (CBr).
Synthesis of 2ꢀ{4ꢀ[pꢀ(3ꢀhydroxynaphthalenꢀ2ꢀyloxy)alkoxy]ꢀ
styryl}quinolines 4a—c (general procedure). Potassium carbonate
(0.18 g, 1.3 mmol) was added to 2,3ꢀdihydroxynaphthalene
(0.40 g, 2.5 mmol) in 2ꢀbutanone (40 mL). The reaction mixture
was refluxed for 30 min with magnetic stirring, then the correꢀ
sponding bromoalkoxystyrylquinoline 2 (n = 2, 4, 5) (0.5 mmol)
was added and the mixture was refluxed for 6—24 h until comꢀ
pound 2 disappeared. The reaction progress was monitored by
TLC (acetone—hexane (1 : 5)). After almost all 2ꢀbutanone was
2ꢀ(E)ꢀ[4ꢀ(2ꢀBromoethoxy)styryl]quinoline (2a). The yield
was 0.18 g (51%), white crystals after recrystallization from hexꢀ
ane, m.p. 135—136 °C. Found (%): C, 64.24; H, 4.68; N, 3.70.
C19H16BrNO. Calculated (%): C, 64.42; H, 4.55; N, 3.95.
1H NMR (CDCl3), δ: 3.67 (t, 2 H, CH2Br, J = 6.3 Hz); 4.34
(t, 2 H, CH2O, J = 6.3 Hz); 6.95 (d, 2 H, oꢀC6H4O, J = 8.7 Hz);
7.30 (d, 1 H, =CH—, J = 16.3 Hz); 7.49 (t, 1 H, quinoline,
J = 7.6 Hz); 7.59 (d, 2 H, mꢀC6H4O, J = 8.7 Hz); 7.62—7.68
(m, 2 H, quinoline, —CH=); 7.71 (t, 1 H, quinoline, J = 7.7 Hz);
7.78 (d, 1 H, quinoline, J = 7.9 Hz); 8.08 (d, 1 H, quinoline,
J = 8.4 Hz); 8.12 (d, 1 H, quinoline, J = 8.6 Hz). IR, ν/cm–1
:

Supramolecular styrylquinolineꢀnaphthol dyads
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 7, July, 2011
1499
evaporated, a dilute hydrochloric acid was added to the reaction
mixture to pH 6. A precipitate that formed was filtered off,
washed with diethyl ether and several portions of aq. acetone,
dried in air, and recrystallized from ethanol.
1629 (C=C), 1598, 1514, 1473, 1260 (COC), 1171, 1113, 979
(—CH=CH).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 10ꢀ03ꢀ00751)
and the Presidium of Russian Academy of Sciences (Proꢀ
gram of Basic Research "Development of Methods for
Preparation of Chemical Compounds and Creation of New
Materials", Subprogram "Polyfunctional Materials for
Molecular Electronics").
2ꢀ(E)ꢀ{4ꢀ[2ꢀ(3ꢀHydroxynaphthalenꢀ2ꢀyloxy)ethoxy]styryl}ꢀ
quinoline (4a). The yield was 0.09 g (42%), a white powder, m.p.
212—213 °C. Found (%): C, 80.54; H, 5.17; N, 3.15. C29H23NO3.
Calculated (%): C, 80.35; H, 5.35; N, 3.23. 1H NMR (DMSOꢀd6),
δ: 4.42—4.48 (m, 4 H, CH2); 7.08 (d, 2 H, oꢀC6H4O, J = 8.8 Hz);
7.16 (s, 1 H, naphthalene); 7.20—7.26 (m, 2 H, naphthalene);
7.31—7.37 (m, 2 H, =CH—, naphthalene); 7.53 (t, 1 H, quinoꢀ
line, J = 7.5 Hz); 7.59 (d, 1 H, naphthalene, J = 6.8 Hz);
7.66—7.74 (m, 4 H, mꢀC6H4O, naphthalene, quinoline); 7.79
(d, 1 H, —CH=, J = 16.3 Hz); 7.83 (d, 1 H, quinoline, J = 8.6 Hz);
7.91 (d, 1 H, quinoline, J = 8.1 Hz); 7.96 (d, 1 H, quinoline,
J = 8.4 Hz); 8.31 (d, 1 H, quinoline, J = 8.6 Hz); 11.05 (br.s, 1 H,
OH). IR, ν/cm–1: 3600—2400 (OH), 3053, 3043, 2944, 2867
(CH2), 1633 (C=C), 1598, 1510, 1452, 1263, 1238 (COC), 1176,
966 (—CH=CH).
References
1. A. P. de Silva, S. Uchiyama, Nature Nanotechnology, 2007,
2, 399.
2. F. M. Raymo, The Spectrum, 2004, 17, 14.
3. D. Gust, T. A. Moore, A. L. Moore, Chem. Commun.,
2006, 1169.
2ꢀ(E)ꢀ{4ꢀ[4ꢀ(3ꢀHydroxynaphthalenꢀ2ꢀyloxy)butoxy]styryl}ꢀ
quinoline (4b). The yield was 0.19 g (82%), a white powder, m.p.
191—192 °C. Found (%): C, 80.44; H, 5.66; N, 2.84. C31H27NO3.
Calculated (%): C, 80.67; H, 5.90; N, 3.03. 1H NMR (DMSOꢀd6),
δ: 1.94—2.04 (m, 4 H, CH2); 4.09—4.23 (m, 4 H, CH2); 7.03
(d, 2 H, oꢀC6H4O, J = 8.4 Hz); 7.15 (s, 1 H, naphthalene);
7.20—7.26 (m, 2 H, naphthalene); 7.28 (s, 1 H, naphthalene);
7.34 (d, 1 H, =CH—, J = 16.3 Hz); 7.54 (t, 1 H, quinoline,
J = 7.6 Hz); 7.61 (d, 1 H, naphthalene, J = 6.7 Hz); 7.65—7.71
(m, 3 H, mꢀC6H4O, naphthalene); 7.74 (t, 1 H, quinoline,
J = 7.6 Hz); 7.79 (d, 1 H, —CH=, J = 16.3 Hz); 7.84 (d, 1 H,
quinoline, J = 8.6 Hz); 7.93 (d, 1 H, quinoline, J = 8.1 Hz); 7.97
(d, 1 H, quinoline, J = 8.3 Hz); 8.32 (d, 1 H, quinoline, J = 8.6 Hz);
9.42 (s, 1 H, OH). IR, ν/cm–1: 3600—2400 (OH), 3057, 3040,
2940, 2857 (CH2), 1635 (C=C), 1597, 1511, 1262, 1236, (COC),
1176, 976 (—CH=CH).
4. H. Tian, S. Wang, Chem. Commun., 2007, 781.
5. K. Szacilowsk, Chem. Rev., 2008, 108, 3481.
6. J. Andreasson, U. Pischel, Chem. Soc. Rev., 2010, 39, 174.
7. M. F. Budyka, H. I. Potashova, T. N. Gavrishova, V. M. Li,
Izv. Akad. Nauk, Ser. Khim., 2008, 2535 [Russ. Chem. Bull.,
Int. Ed., 2008, 57, 2586].
8. M. F. Budyka, N. I. Potashova, T. N. Gavrishova, V. M. Li,
J. Mater. Chem., 2009, 19, 7721.
9. M. F. Budyka, Khim. Vysokikh Energyii, 2010, 44, 154 [High
Energy Chem. (Engl. Transl.), 2010, 44].
10. G. Galiazzo, P. Bortolus, G. Gennari, Gazz. Chim. Ital.,
1990, 120, 581.
11. N. Agmon, W. Rettig, C. Groth, J. Am. Chem. Soc., 2002,
124, 1089.
12. C. Garcia, A. Aubry, A. Collet, Bull. Soc. Chim. Fr., 1996,
133, 853.
2ꢀ(E)ꢀ{4ꢀ[5ꢀ(3ꢀHydroxynaphthalenꢀ2ꢀyloxy)pentoxy]styryl}ꢀ
quinoline (4c). The yield was 0.20 g (85%), a white powder, m.p.
>180 °C (decomp.). Found (%): C, 80.66; H, 6.23; N, 2.80.
C32H29NO3. Calculated (%): C, 80.82; H, 6.15; N, 2.95. 1H NMR
(DMSOꢀd6), δ: 1.61—1.72 (m, 2 H, CH2); 1.81—1.95 (m, 4 H,
CH2); 4.08 (t, 2 H, CH2, J = 6.4 Hz); 4.13 (t, 2 H, CH2, J = 6.4 Hz);
7.02 (d, 2 H, oꢀC6H4O, J = 8.6 Hz); 7.14 (s, 1 H, naphthalene);
7.20—7.28 (m, 3 H, naphthalene); 7.34 (d, 1 H, =CH—,
J = 16.3 Hz); 7.52—7.61 (m, 3 H, naphthalene, quinoline); 7.69
(d, 2 H, mꢀC6H4O, J = 8.6 Hz); 7.74 (t, 1 H, quinoline, J = 7.5 Hz);
7.80 (d, 1 H, —CH=, J = 16.3 Hz); 7.84 (d, 1 H, quinoline,
J = 8.6 Hz); 7.94 (d, 1 H, quinoline, J = 7.9 Hz); 7.98 (d, 1 H,
quinoline, J = 8.3 Hz); 8.33 (d, 1 H, quinoline, J = 8.6 Hz). IR,
ν/cm–1: 3600—2400 (OH), 3061, 3038, 2951, 2866 (CH2),
13. J. A. Stafford, N. L. Valvano, J. Org. Chem., 1994, 59, 4346.
14. F.ꢀC. Huang, R. A. Galemmo, H. F. Campbell, US Pat.
4918081, 1990; Chem. Abstr., 1990, 113, 97461.
15. T. N. Gavrishova, V. M. Li, K. V. Gor´kov, M. F. Budyꢀ
ka, Zh. Prikl. Khim., 2011, 84, 516 [Russ. J. Appl. Chem.
(Engl. Transl.), 2011, 84].
16. L. Nagarapu, A. A. Satyender, G. Chandana, R. Bantu,
J. Heterocycl. Chem., 2009, 46, 195.
17. M. Schmidt, J. Ungvari, J. Gloede, B. Dobner, A. Langner,
Bioorg. Med. Chem. Lett., 2007, 15, 2283.
Received March 4, 2011;
in revised form April 11, 2011