Synthesis and properties of first bis(fluoreno)crownophanes

Article abstract of DOI:10.1007/s11178-005-0138-6

Alkylation of 2,7-dihydroxy-9H-fluoren-9-one with 2-(2-chloroethoxy) ethanol, 2-[2-(2-chloroethoxy)-ethoxy]ethanol, and 2-{2-[2-(2-chloroethoxy) ethoxy]ethoxy}ethanol in dimethylformamide in the presence of potassium carbonate gave 78-80% of the correspon

Full text of DOI:10.1007/s11178-005-0138-6

Russian Journal of Organic Chemistry, Vol. 41, No. 1, 2005, pp. 144-150. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005,
pp. 144-149.
Original Russian Text Copyright Ó 2005 by Lyapunov, Kirichenko, Kulygina, Luk'yanenko.
Synthesis and Properties of First Bis(fluoreno)crownophanes
A. Yu. Lyapunov, T. I. Kirichenko, E. Yu. Kulygina, and N. G. Luk’yanenko
Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine,
Lyustdorfskaya doroga 86, Odessa, 65080 Ukraine
Received May 15, 2004
Abstract—Alkylation of 2,7-dihydroxy-9H-fluoren-9-one with 2-(2-chloroethoxy)ethanol, 2-[2-(2-chloroethoxy)-
ethoxy]ethanol, and 2-{2-[2-(2-chloroethoxy)ethoxy]ethoxy}ethanol in dimethylformamide in the presence of
potassium carbonate gave 78–80% of the corresponding diols which were treated with p-toluenesulfonyl chloride
in a dioxane–chloroform mixture in the presence of triethylamine at 0–5°C (30 h). The resulting bis(p-toluene-
sulfonates) were brought into condensation with 2,7-dihydroxy-9H-fluoren-9-one in a very dilute solution in
dimethylformamide containing anhydrous potassium carbonate at 80–85°C.Appropriate treatment of the reaction
mixture, followed by chromatographic purification afforded 53–27% of the first representatives of a new class of
cyclophanes, bis(oxofluoreno)crownophanes. Raising the temperature to 95–105°C resulted in an appreciable
decrease of the product yield. The yield of the target products did not increase on replacement of potassium
carbonate by cesium carbonate.
Cyclophanes are macrocyclic compounds incorporat-
ing one or several aromatic fragments [1]. They show
enhanced selectivity in complex formation and constitute
one of the main classes of macrocyclic receptors.
Cyclophanes are widely used as catalysts, ion and neutral
molecule carriers, chemosensors [2], and components of
supramolecular structures like rotaxanes and catenanes,
the latter being basis structures in the design of nano-
electronic devices [3]. Crownophanes in which large
aromatic fragments are linked through polyoxaethylene
bridges attract specific attention. Crownophanes success-
fully combine properties of classical crown ethers and
cyclophanes. Such a symbiosis makes them excellent
receptors for both ionic and neutral species [4]. It is also
important that flexible polyether chains allow relatively
easy adjustment of the shape and size of the
intramolecular cavity of crownophanes to meet steric
requirements of a substrate.
powerful cumulative effect which in most cases is
responsible for the three-dimensional chemical structure
and properties of complexes [5, 6]. With the goal of
controlling complexing properties of cyclophanes, large
and (as a rule) nonpolar aromatic fragments were
introduced into the macrocyclic framework. On the other
hand, to enhance intermolecular interactions which
generally have electrostatic origin [5], it seems reasonable
to introduce into the macroring large aromatic fragments
with an extended p-electron system, containing polar
groups. In this respect, it may be promising to incorporate
into the crownophane structure a fluorenone fragment
which was not used previously for such purposes. This
assumption is based on the following: (1) Fluorenone
possesses a large, strongly polarized p-electron system
which is capable of effectively reacting with cations and
other aromatic systems; (2) the carbonyl oxygen atom in
fluorenone is a strong hydrogen acceptor which could
give rise to strong hydrogen bonds with substrates,
whereas hydrogen bonding is known to be often the
crucial factor in molecular recognition processes and self-
organization of supramolecular systems; (3) the carbonyl
group in fluorenone can act as an antenna capable of
recognizing an electron-deficient guest species, directing
it toward the macrocyclic cavity of the host, and stabilizing
the intercalation via electrostatic interactions; (4) fluore-
none and its derivatives exhibit good luminescent
The structure, selectivity of formation, and stability of
molecular complexes and supramolecular systems are
determined by various intermolecular nonvalence
interactions [5]. Among these, the most important are
hydrogen bonding, electrostatic interactions, p–p stacking,
interactions like p–cation, p··· H–C, and p···H–O,
hydrophobic effects, and van der Waals forces. All these
interactions taken alone are weak, but they give rise to a
1070-4280/05/4101-0144Ó2005 Pleiades Publishing, Inc.

SYNTHESIS AND PROPERTIES OF FIRST BIS(FLUORENO)CROWNOPHANES
145
properties which may be important in the design of high-
sensitive fluorescent chemosensors; and finally (5) the
carbonyl group in fluorenonophanes can readily be
converted into other functional groups, thus providing the
possibility for fine tuning of the complexing power of such
macrocyclic receptors.
(0–5°C, 30 h). As a result, we obtained the corresponding
bis(p-toluenesulfonates) IVa–IVc in a good yield (70–
88%). The latter were brought into condensation with
dihydroxyfluorenone I in a strongly dilute DMF solution
in the presence of anhydrous potassium carbonate (80–
85°C). After appropriate treatment and chromatographic
purification, we isolated bis(oxofluoreno)crownophanes.
When the condensation was carried out at higher
temperature (95–105°C), the yield of compounds Va–
Vc was appreciably lower. It is known [8] that cesium
cation favors formation of many macrocyclic systems.
However, we failed to increase the yield of the target
products to an appreciable extent by replacement of
potassium carbonate by cesium carbonate. Presumably,
in this case the effect of the cation is either weak or
absent.
The present communication describes the synthesis
and spectral properties of the first representatives of
a new cyclophane family, bis(oxofluoreno)crownophanes
Va–Vc. As starting compound we used relatively
accessible 2,7-dihydroxy-9H-fluoren-9-one (I) [7]. Its
alkylation with monochloro derivatives of di-, tri-, and
tetraethylene glycols (compounds IIa–IIc) in DMF in
the presence of potassium carbonate gave diols IIIa–
IIIc in 78–80% yield (Scheme 1). Diols IIIa–IIIc were
treated with p-toluenesulfonyl chloride in a mixture of
dioxane and chloroform using triethylamine as a base
Crownophane Va was isolated in a considerably
greater yield than those of compounds Vb and Vc; the
Scheme 1.
2
2
+2
2+
2
. &2 ꢀ'0)ꢁꢂ
ꢃꢄꢂKꢁꢂꢅꢄ ꢅꢆ
2
2
&O
2
2
2+
2+
2
2+
,,D ,,F
,
2
2
,,,D ,,F
2
2
2
2
27V
2
2
2
7V&Oꢀ1(W ꢁꢂ& + 2 &+&O ꢁ
ꢇꢄꢂKꢁꢂꢄ ꢆ &
2
,ꢁꢂ. &2 ꢀ'0)ꢁꢂꢃꢄꢂKꢁꢂꢅꢄ ꢅꢆ &
2
2
2
27V
2
2
2
2
2
2
,9D ,9F
9Dꢁꢂꢆꢇꢈꢉꢂ9Eꢁꢂꢊꢋꢈꢉꢂ9Fꢁꢂꢇꢄꢈ
n= 0 (a), 1 (b), 2 (c).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

146
LYAPUNOV et al.
satisfactorily describe the real structure of crownophanes
Va–Vc at least in the gas phase.
2
2
2
2
According to the calculations, an anti conformation
with almost coplanar arrangement of the partially
overlapping fluorene fragments is the most favorable for
crownophanes Va–Vc. The absence of clearly defined
intramolecular cavity in Va–Vc is not a serious obstacle
to formation of intercalation compounds like
pseudorotaxanes [13]. Bonding intramolecular p–p
interactions between the aromatic fragments (which are
unfavorable from the viewpoint of entropy factor) in
solution may be lacking due to restriction of the internal
mobility of the molecule. In this case, a dynamic equilibrium
between numerous conformations of the macroring
should be established, and these conformations may
include those with an open cavity whose shape and size
may vary over a fairly wide range to fit steric requirements
of a substrate.
2
2
2
2
2
2
27V
$
yields of the two latter were approximately similar. The
observed difference may be attributed to formation of
quasicyclic structure A (which is ready to cyclization) as
a result of intramolecular p–p stacking of the fluorene
fragments in intermediate open-chain compound. As we
showed in preliminary communication [9], an analogous
interaction was revealed in crystalline compound Vb; it
is also typical of structures related to fluorenone, e.g.,
dibenzofurans [10]. In keeping with the entropy factor,
such preorganization is more probable for molecules with
short bridges between the fluorene fragments. As the
length of the bridge increases, the number of degrees of
freedom of the molecule also rises, and its preorganization
becomes less favorable. As a result, the yield of crowno-
phanes Vb and Vc decreases.
The above stated is confirmed by analysis of the
1H NMR spectra of crownophanes Va–Vc, which
displayed a set of signals typical of oligoethylene glycol
fragments in the region d 3.65–4.10 ppm and aromatic
proton signals characteristic of 2,7 disubstituted
fluorenones (Fig. 2). As compared to 2,7-dimethoxy-
fluorenone VI taken as model compound, signals from
all fluorene protons in the spectra of Va–Vc are displaced
upfield by 0.16–0.39 ppm due to shielding by the opposite
aromatic fragment (see table). Regardless of the
macroring size, the largest upfield shift is observed for
the Ha and Hc protons relative to the corresponding shift
of the Hb signal. These data indicate fast (on the NMR
time scale, 300 MHz) rotation of the fluorene fragments
with respect to each other. Computer simulation
(Spartan’02, MMFF force field [12]) showed that such
rotation makes the Ha and Hc protons the most shielded
and that the average distance from these protons to the
plane of the opposite aromatic fragment does not depend
on the ring size to an appreciable extent.
The fluorene fragments in molecule Vb in crystal are
arranged parallel to each other at a distance of 3.45A[9],
°
which is typical of cyclophanes if p–p stacking exists
[11]. Mutual orientation of the carbonyl groups cor-
responds to nonpolar anti conformation of the molecule.
The crystalline structure of compound Vb is well consistent
with the most favorable theoretical structure determined
by conformational analysis in terms of the Monte Carlo
procedure (Spartan’02 software package, MMFF force
field [12]; Fig. 1). The mean-square deviation of the
coordinates of all non-hydrogen atoms in the calculated
°
structure from those determined experimentally is 1.55 A
. Therefore, the above calculation method is believed to
Thus we have synthesized the first representatives of
a new crownophane series, which are promising as
9
9
9
Va
Vb
Vc
Fig. 1. Calculated structures of crownophanes Va–Vc.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

SYNTHESIS AND PROPERTIES OF FIRST BIS(FLUORENO)CROWNOPHANES
147
+
macrocyclic receptors for small organic molecules and
metal ions. Complexing power of these compounds will
be the subject of our further studies.
+
20H
0H2
EXPERIMENTAL
+
2
9,
1
The H NMR spectra were recorded on a Varian
VXR-300 spectrometer at 300 MHz. The mass spectra
(electron impact, 70 eV) were obtained on an MKh-1321
instrument with direct sample admission into the ion
source (ion source temperature 200°C). The IR spectra
were measured in KBr using a Specord IR spectrometer.
The UV spectra were recorded on a Specord-40
spectrophotometer.
+
ꢀ
ꢀ
+
ꢀ
+
9Dꢀ
ꢀ
+ ꢁꢀ+
Silica gel L (250 mm, Chemapol) was used for
preparative column chromatography. The purity of the
products was checked by TLC on Silufol UV 254 plates.
Compounds IIa and IIb were commercial products, and
compounds IIc [14] and VI [15] were prepared by known
procedures.
ꢀ
+
ꢀ
9E
ꢀ
+
ꢀ
+ ꢁꢀ+
Diols IIIa–IIIc (general procedure). 2,7-Di-
hydroxy-9H-fluoren-9-one (I), 16.96 g (80 mmol), was
added under argon to a suspension of freshly calcined
potassium carbonate, 66.24 g (480 mmol), and sodium
iodide, 24 g (160 mmol), in 400 ml of anhydrous dimethyl-
formamide. The mixture was stirred for 1 h at 80°C,
240 mol of compound IIa–IIc was added, and the mixture
was stirred for 35 h at that temperature. It was then
filtered, and the filtrate was evaporated to dryness under
reduced pressure. The residue was dissolved in
chloroform, and the solution was washed with a 5%
aqueous solution of sodium hydroxide and two portions
of water, dried over anhydrous magnesium sulfate, and
evaporated under reduced pressure. The residue was
recrystallized from 2-propanol to isolate compounds IIIa–
IIIc as orange–red crystals.
9Fꢀ
ꢀ
+
ꢀ
+
ꢀ
+
ꢀ
+
9,ꢀ
ꢀꢀꢀꢀꢀꢂꢃꢄꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢂꢃꢅꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢂꢃꢆꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢂꢃꢇꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢄꢃꢈꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢄꢃꢄꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁꢀꢀSꢀꢀSꢀꢀPꢀꢀ
G
1
Fig. 2. Fluorene proton region in the H NMR spectra of
compounds Va–Vc and VI (DMSO-d6, 25°C)
Relative chemical shifts of protons in the fluorene fragment of
2,7-dimethoxyfluorenone (VI) and crownophanes Va–Vc
(DMSO-d6, 25°C)
'LIIHUHQFH LQ WKH FKHPLFDO
2,7-Bis[2-(2-hydroxyethoxy)ethoxy]-9H-fluoren-
9-one (IIIa). Yield 24.2 g (78%), mp 117–119°C. UV
spectrum (CH3OH), lmax, nm (log e): 270 (5.0), 469
&KHPLFDO VKLIWV Gꢀ SSP
&RPSꢁ
QRꢁ
VKLIWV 'Gꢀ SSP
+
+
+
+
+
+
1
(2.43). IR spectrum: n(C=O) 1700 cm-1. H NMR
ꢂꢁꢂꢂ
ꢂꢁꢅꢃ
ꢂꢁꢃꢄ
ꢂꢁꢃꢇ
ꢅꢁꢆꢅ
ꢅꢁꢆꢆ
±ꢇꢁꢈꢉ
±ꢇꢁꢊꢅ
±ꢇꢁꢆꢂ ±ꢇꢁꢈꢆ
±ꢇꢁꢊꢆ ±ꢇꢁꢈꢅ
9Dꢀ
9Eꢀ
9Fꢀ
9,ꢀ
spectrum (CDCl3), d, ppm: 1.97 br.s (2H, OH), 3.65–
3.72 m (4H, CH2O), 3.74–3.82 m (4H, CH2O), 3.84–
3.92 m (4H, CH2O), 4.14–4.21 m (4H, CH2O), 6.97 d.d
(2H, Hb, J = 8.09 Hz), 7.17 d (2H, Ha, J = 2.18 Hz), 7.29 d
(2H, Hc, J = 8.09 Hz). Mass spectrum, m/z (Irel, %):
388 [M]+ (44), 300 (7), 212 (35). Found, %: C 65.19;
H 6.29. C21H24O7. Calculated, %: C 64.94; H 6.23.
aꢂꢁꢃꢋ aꢂꢁꢃꢋ
ꢅꢁꢇꢄ ꢅꢁꢇꢆ
ꢅꢁꢆꢃ aꢌ±ꢇꢁꢊꢆꢍ aꢌ±ꢇꢁꢆꢅꢍ ±ꢇꢁꢈꢇ
ꢅꢁꢋꢃ
±
±
±
a
For designation of protons, see Fig. 2.
b
Dd = d(VI) – d(V).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

148
LYAPUNOV et al.
2,7-Bis{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}-
CH2O, J = 4.82 Hz), 6.95 d.d (2H, Hb, J = 8.10 Hz), 7.12 d
(2H, Ha, J = 2.18 Hz), 7.27–7.36 m (6H, Harom, Hc), 7.80 d
(4H, Harom, J = 8.09 Hz). Mass spectrum, m/z (Irel, %):
696 [M]+ (5), 524 (26), 497 (7), 282 (10), 212 (31). Found,
%: C 60.47; H 5.41. C35H36O11S2. Calculated, %: C 60.33;
H 5.21.
9H-fluoren-9-one (IIIb). Yield 29.3 g (77%), mp 91–
92°C. UV spectrum (CH3OH), lmax, nm (log e): 270
(4.95), 473 (2.53). IR spectrum: n(C=O) 1700 cm-1.
1H NMR spectrum (CDCl3), d, ppm: 2.18 br.s (2H, OH),
3.63 t (4H, CH2O, J = 4.2 Hz), 3.68–3.82 m (12H, CH2O),
3.87 t (4H, CH2O, J = 4.5 Hz), 4.17 t (4H, CH2O, J =
4.5 Hz), 6.98 d.d (2H, Hb, J = 8.09 Hz), 7.17 d (2H, Ha,
J = 2.18 Hz), 7.28 d (2H, Hc, J = 8.09 Hz). Mass
spectrum, m/z (Irel, %): 476 [M]+ (41), 432 (3), 344 (3),
212 (11). Found, %: C 62.82; H 6.65. C25H32O9.
Calculated, %: C 63.01; H 6.77.
2-(2-{2-[7-(2-{2-[2-(4-Methylphenylsulfonyloxy)-
ethoxy]ethoxy}ethoxy)-9-oxo-9H-fluoren-2-yloxy]-
ethoxy}ethoxy)ethyl 4-methylbenzenesulfonate
(IVb). Dark red oily substance which crystallizes under
a layer of hexane. Yield 19.7 g (84%), mp 68–70°C. UV
spectrum (1,4-dioxane), lmax, nm (log e): 225 (4.72), 272
(5.14), 301 (4.10), 314 (4.08), 469 (2.71). IR spectrum:
n(C=O) 1700 cm-1. 1H NMR spectrum (CDCl3), d, ppm:
2.43 s (6H, Me), 3.57–3.75 m (12H, CH2O), 3.79–
3.87 m (4H, CH2O), 4.08–4.21 m (8H, CH2O), 6.97 d.d
(2H, Hb, J = 8.10 Hz), 7.15 d (2H, Ha, J = 2.49 Hz), 7.29 d
(2H, Hc, J = 8.10 Hz), 7.33 d (4H, Harom, J = 8.25 Hz),
7.80 d (4H, Harom, J = 8.35 Hz). Mass spectrum, m/z (Irel,
%): 524 (4), 212 (16), 199 (75), 155 (49). Found, %:
C 59.56; H 5.47. C39H44O13S2. Calculated, %: C 59.68;
H 5.65.
2,7-Bis(2-{2-[2-(2-hydroxyethoxy)ethoxy]-
ethoxy}ethoxy)-9H-fluoren-9-one (IIIc). Yield
36.1 g (80%), mp 61–63°C. UV spectrum (CH3OH),
l
max, nm (log e): 270 (4.89), 300 (3.83), 312 (8.30), 469
1
(2.47). IR spectrum: n(C=O) 1700 cm-1. H NMR
spectrum (CDCl3), d, ppm: 2.07 br.s (2H, OH), 3.61 t
(4H, CH2O, J = 4.51 Hz), 3.65–3.77 m (20H, CH2O),
4.17 t (4H, CH2O, J = 4.67 Hz), 4.28 t (4H, CH2O, J =
4.67 Hz), 6.97 d.d (2H, Hb, J = 8.09 Hz), 7.17 d (2H, Ha,
J = 2.49 Hz), 7.28 d (2H, Hc, J = 8.10 Hz). Mass
spectrum, m/z (Irel, %): 564 [M]+ (14), 388 (2), 212 (10).
Found, %: C 61.87; H 6.94. C29H40O11. Calculated, %:
C 61.69; H 7.14.
2-{2-[2-(2-{7-[2-(2-{2-[2-(4-Methylphenyl-
sulfonyloxy)ethoxy]ethoxy}ethoxy)ethoxy]-9-oxo-
9H-fluoren-2-yloxy}ethoxy)ethoxy]ethoxy}ethyl 4-
methylbenzenesulfonate (IVc). Dark red oily sub-
stance. Yield 18.3 g (70%). UV spectrum (1,4-dioxane),
Bis(p-toluenesulfonates) IVa–IVc (general
procedure). A solution of 75 mol of p-toluenesulfonyl
chloride in 30 ml of anhydrous dioxane was added
dropwise over a period of 2 h to a solution of 30 mmol of
diol IIIa–IIIc and 90 mmol of triethylamine in 120 ml of
chloroform, maintained at 0–5°C. The cooling bath was
removed, and the mixture was stirred for 30 h at room
temperature. It was then diluted with an equal volume of
chloroform, and the resulting solution was washed in
succession with 5% hydrochloric acid, 10% aqueous
ammonia, water, and a saturated solution of sodium
chloride, dried over anhydrous magnesium sulfate, and
evaporated under reduced pressure. The residue was
treated as indicated below.
lmax, nm (log e): 229 (4.40), 272 (4.96), 302 (3.88), 314
(3.87), 464 (2.64). IR spectrum: n(C=O) 1700 cm-1.
1H NMR spectrum (CDCl3), d, ppm: 2.43 s (6H, Me),
3.60 s (8H, CH2O), 3.62–3.76 m (12H, CH2O), 3.85 t
(4H, CH2O, J = 4.67 Hz), 4.11–4.20 m (8H, CH2O),
6.97 d.d (2H, Hb, J = 8.09 Hz), 7.15 d (2H, Ha, J =
2.18 Hz), 7.28 d (2H, Hc, J = 8.10 Hz), 7.33 d (4H, Harom
,
J = 8.11 Hz), 7.79 d (4H, Harom, J = 8.10 Hz). Mass
spectrum, m/z (Irel, %): 414 (3), 212 (8), 199 (4), 155 (4).
Found, %: C 58.98; H 5.83. C43H52O15S2. Calculated,
%: C 59.16; H 6.00.
Crownophanes Va–Vc (general procedure).
A solution of 2.12 g (10 mmol) of compound I and
10 mmol of bis(p-toluenesulfonate) IVa–IVc in 400 ml
of anhydrous DMF was added dropwise under stirring
over a period of 10 h to a suspension of 5.52 g (0.04 mol)
of dry potassium carbonate in 600 ml of anhydrous DMF,
maintaining the temperature at 80°C. When the addition
was complete, the mixture was stirred for 40 h at that
temperature, cooled, and filtered, and the solvent was
distilled off from the filtrate under reduced pressure. The
2-[2-(7-{2-[2-(4-Methylphenylsulfonyloxy)-
ethoxy]ethoxy}-9-oxo-9H-fluoren-2-yloxy)-
ethoxy]ethyl 4-methylbenzenesulfonate (IVa).
Orange crystals from 2-propanol. Yield 18.4 g (88%),
mp 109–112°C. UV spectrum (1,4-dioxane), lmax, nm
(log e): 272 (4.96), 301 (3.90), 314 (3.88), 464 (2.57). IR
”1
1
spectrum: n(C=O) 1700 cm . H NMR spectrum
(CDCl3), d, ppm: 2.42 s (6H, Me), 3.73–3.83 m (8H,
CH2O), 4.07 t (4H, CH2O, J = 4.52 Hz), 4.21 t (4H,
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

SYNTHESIS AND PROPERTIES OF FIRST BIS(FLUORENO)CROWNOPHANES
149
(4H, Hc, J = 8.40 Hz). Mass spectrum, m/z (Irel, %): 740
[M]+ (100), 369 (5), 238 (17), 212 (21), 129 (22). Found,
%: C 68.34; H 6.22. C42H44O12. Calculated, %: C 68.10;
H 5.99.
residue was combined with the precipitate, washed with
two portions of methanol (50 and 30 ml), placed into a
Soxhlet apparatus, and continuously extracted with
toluene over a period of 40 h. The extract was cooled to
room temperature, and the precipitate was filtered off
and repeatedly crystallized from toluene until complete
extraction of the product. The toluene mother liquors were
combined and evaporated under reduced pressure, and
the residue was washed with acetone (4´5 ml), dried,
and purified by column chromatography on silica gel using
chloroform–methanol (100:1) as eluent.
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8 , 11 , 1 4 , 2 6 , 2 9 , 3 2 - H e x a o x a h e p t a c y c l o -
[31.3.1.13,7.115,19.121,25.04,36.018,22]tetraconta-
1(37),3(40),4,6,15(39),16,18,21(38),22,24,33,35-
dodecaene-2,20-dione (Va). Orange–red crystals.
Yield 2.98 g (53%), mp 296–298°C (decomp.). UV
spectrum (1,4-doxane), lmax, nm (log e): 264 (5.08), 302
(4.05), 314 (4.04), 473 (2.71). IR spectrum: n(C=O)
1
1700 cm-1. H NMR spectrum (DMSO-d6), d, ppm:
3.81 t (8H, CH2O, J = 3.12 Hz), 4.09 t (8H, CH2OAr,
J = 3.12 Hz), 6.66 br.s (4H, Ha), 6.84 d.d (4H, Hb, 3J =
8.10, 4J = 2.17 Hz), 7.16 d (4H, Hc, J = 8.10 Hz). Mass
spectrum, m/z (Irel, %): 564 [M]+ (100), 282 (7), 239 (8),
212 (11), 45 (8). Found, %: C 72.26; H 5.25. C34H28O8.
Calculated, %: C 72.33; H 5.00.
8,11,14,17,29,32,35,38-Octaoxaheptacyclo-
[37.3.1.13,7.118,22.124,28.04,42.021,25]hexatetraconta-
1(43),3(46),4,6,18(45),19,21,24,25,27,39,41-
dodecaene-2,23-dione (Vb). Light red crystals. Yield
1.76 g (27%), mp 197–199°C. UV spectrum (1,4-di-
oxane), lmax, nm (loge): 264 (5.09), 302 (4.06), 314 (4.04),
470 (2.66). IR spectrum: n(C=O) 1700 cm-1. 1H NMR
spectrum (DMSO-d6), d, ppm: 3.65 s (8H, CH2O),
3.75 t (8H, CH2O, J = 4.20 Hz), 4.04 t (8H, CH2O, J =
4.20 Hz), 6.81 br.s (4H, Ha), 6.84 br.d (4H, Hb, J =
8.10 Hz), 7.15 d (4H, Hc, J = 8.10 Hz). Mass spectrum,
m/z (Irel, %): 652 [M]+ (100), 580 (16), 326 (14), 212
(18). Found, %: C 69.77; H 5.69. C38H36O10. Calculated,
%: C 69.93; H 5.56.
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8,11,14,17,20,32,35,38,41,44-Decaoxahepta-
cyclo[43.3.1.13,7.121,25.127,31.04,48.024,28]dopentaconta-
1(49),3(52),4,6,21(51),22,24,27(50),28,30,45,47-
dodecaene-2,26-dione (Vc). Orange–red crystals.
Yield 2.22 g (30%), mp 176–177°C (from toluene). UV
spectrum (1,4-dioxane), lmax, nm (loge): 263 (5.13), 270
(5.08), 302 (4.10), 314 (4.08), 468 (2.76). IR spectrum:
n(C=O) 1700 cm-1. 1H NMR spectrum (CDCl3), d, ppm:
3.73 br.s (16H, CH2O), 3.87 t (8H, CH2O, J = 4.53 Hz),
4.00 t (8H, CH2O, J = 4.53 Hz), 6.76 d.d (4H, Hb, 3J =
8.40, 4J = 2.18 Hz), 6.89 d (4H, Ha, J = 2.18 Hz), 6.97 d
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