Synthesis and properties of first representatives of crownophanes containing the fluorenone and naphthalene fragments

Article abstract of DOI:10.1007/s11172-007-0149-2

A new family of crownophanes containing the fluorenone and naphthalene fragments linked by oligo(oxyethylene) bridges were synthesized. Reactions of these ligands with the paraquat dication gave inclusion complexes of the pseudorotaxane type that were det

Full text of DOI:10.1007/s11172-007-0149-2

Russian Chemical Bulletin, International Edition, Vol. 56, No. 5, pp. 986—992, May, 2007
986
Synthesis and properties of first representatives of crownophanes
containing the fluorenone and naphthalene fragments
N. G. Lukyanenko,ꢀ A. Yu. Lyapunov, and T. I. Kirichenko
A. V. Bogatskii Physicochemical Institute, National Academy of Sciences of the Ukraine,
86 Lyustdorfskaya Doroga, 65080 Odessa, Ukraine.
Eꢀmail: ngl@farlep.net
A new family of crownophanes containing the fluorenone and naphthalene fragments
linked by oligo(oxyethylene) bridges were synthesized. Reactions of these ligands with the
paraquat dication gave inclusion complexes of the pseudorotaxane type that were detected by
1
FAB mass spectrometry, H NMR spectroscopy, and electronic absorption spectroscopy.
Key words: crownophane, fluorenone, naphthalene, paraquat, pseudorotaxane.
Design, synthesis, and application of various macroꢀ
in the presence of K2CO3 or in EtOH in the presence of
KOH gave diols 4a—c or 4d in 78—80% yields. Reactions
of these diols with pꢀtoluenesulfonyl chloride in a mixture
of 1,4ꢀdioxane and chloroform in the presence of Et3N at
0—5 °C for 30 h afforded ditosylates 5a—d in good
yields (70—88%). The latter reacted with 1,5ꢀdihydroxyꢀ
naphthalene 6 at high dilution in DMF in the presence
of K2CO3. After workup of the reaction mixture and puriꢀ
fication by column chromatography, we obtained fluoreꢀ
noneꢀcontaining crownophanes 1a—d in moderate yields.
The yield of the smallest crownophane 1a was low; the
yields of crownophanes 1b—d were virtually independent
of the ring size.
cyclic receptors that can selectively discriminate between
metal ions, anions, and organic molecules belong to the
main problems of the chemistry of "guest—host" comꢀ
plexes. Cyclophanes, which are macrocycles containing
two or more aromatic fragments linked by various bridges,
hold a central position among such receptors.1—6 The
size, shape, charge, and hydrophobicity of a cyclophane,
as well as its tendency toward various intermolecular inꢀ
teractions with a guest molecule, can be easily changed by
introduction in the receptor structure of rationally seꢀ
lected aromatic fragments, bridges between them, and
functional groups, which allows effective control of its
complexing properties. Because of this, cyclophanes are
widely used in membrane transport and as catalysts, senꢀ
sors, and components of catenanes and rotaxanes that are
prototypes of molecular machines and nanoelectronic
devices.7—15
Recently,16—22 we have described the syntheses and
properties of first representatives of fluorenonophanes
containing two fluorenone fragments or the fluorenone
and stilbene fragments linked by flexible polyether chains
or conformationally rigid pꢀxylylene bridges. We have
demonstrated that fluorenonophanes form stable incluꢀ
sion complexes with electronꢀdeficient organic molꢀ
ecules16—20 and are promising templates for selfꢀassembly
of [2]catenanes on their basis.21,22
1
The H NMR spectra of crownophanes 1a—d show
a set of signals at δ 3.65—4.38, which are typical of
oligo(ethylene glycol) fragments, a characteristic set of
signals (two doublets and a doublet of doublets) for the
fluorenone protons, and a triplet and two doublets for the
naphthalene protons. The signals for all the aromatic proꢀ
tons in crownophanes 1a—d are shifted upfield comꢀ
pared to their positions in the spectra of model comꢀ
pounds: 2,7ꢀdimethoxyfluorenone (7) and 1,5ꢀdimethoxyꢀ
naphthalene (8) (Table 1). This is probably due to reꢀ
ciprocal shielding by the opposite aromatic fragments.
The largest shifts of the signals for these protons were
observed for the smallest crownophane 1a. With an inꢀ
crease in the ring size, the relative shifts of the aforemenꢀ
tioned signals decrease. The signals for the H(4) and
H(8) protons of the naphthalene ring and for the Hc proꢀ
ton of fluorenone show the largest upfield shifts in the
1H NMR spectra of crownophanes 1a—d. The considerꢀ
able upfield shifts for all the aromatic protons in comꢀ
pounds 1 suggest that they exist in solutions mainly as
conformers with contiguous aromatic fragments arranged
parallel or nearly parallel to each other.
Here we describe the synthesis and properties of new
crownophanes containing the fluorenone and naphthaꢀ
lene fragments connected by oligo(oxyethylene) chains
with different lengths.
Crownophanes 1a—d were obtained as shown in
Scheme 1.
Alkylation of 2,7ꢀdihydroxyꢀ9Hꢀfluorenꢀ9ꢀone 2 23
with oligo(ethylene glycol) chlorohydrins 3a—d in DMF
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 951—957, May, 2007.
1066ꢀ5285/07/5605ꢀ0986 © 2007 Springer Science+Business Media, Inc.

Crownophanes with fluorenone and naphthalene
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
987
Scheme 1
n = 0 (a), 1 (b), 2 (c), 3 (d)
i. K2CO3/DMF (KOH/EtOH), 80 °C; ii. TsCl/NEt3, 1,4ꢀdioxane—CHCl3, 0—5 °C, 30 h; iii. K2CO3/DMF, 80 °C.
studied electronꢀwithdrawing guests that form stable inꢀ
clusion complexes with donor macrocyclic molecules.
In particular, a great number of pseudorotaxanes and
rotaxanes have been reported to be complexes of paraquat
ions with crown ethers, cryptands, cyclophanes, and other
macrocyclic host molecules.24—28 Crownophanes 1a—d
containing two πꢀelectronꢀdonating aromatic fragments
should also be "good" hosts for dication 9.
We tried to obtain such complexes under the condiꢀ
tions of competitive complex formation and qualitatively
estimated their relative stabilities by FAB mass spectromꢀ
etry.29—31 Mass spectra were recorded for solutions of
equimolar amounts of crownophanes 1a—d and four
equivalents of paraquat 9•2PF6 in 3ꢀnitrobenzyl alcohol.
In the case of compounds 1b—d with triꢀ, tetraꢀ, and
penta(ethylene glycol) bridges between the aromatic fragꢀ
Paraquat dication 9 and its derivatives (N,N´ꢀdialkylꢀ
4,4´ꢀbipyridinium salts) belong to the most frequently

988
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Lukyanenko et al.
Table 1. Absolute (δ) and relative chemical shifts (∆δ) of the aromatic protons of crownophanes 1a—d and model comꢀ
pounds 7 and 8
Compound
Ha
Hb
Hc
H(2), H(6)
H(3), H(7)
H(4), H(8)
δ
–∆δ
δ
–∆δ
δ
–∆δ
δ
–∆δ
δ
–∆δ
δ
–∆δ
1a
1b
1c
1d
7
6.91
6.92
7.01
7.05
7.16
—
0.25
0.24
0.15
0.11
—
6.81
6.85
6.83
6.84
6.94
—
0.13
0.09
0.11
0.10
—
6.88
6.80
6.94
7.03
7.29
—
0.41
0.49
0.35
0.26
—
6.48
6.57
6.63
6.68
—
0.35
0.26
0.20
0.15
—
7.06
7.08
7.16
7.23
—
0.30
0.28
0.20
0.13
—
7.34
7.58
7.71
7.74
—
0.49
0.25
0.12
0.09
—
8
—
—
—
6.83
—
7.36
—
7.83
—
ments, the mass spectra show peaks due to successive
losses of the hexafluorophosphate anion from 1 : 1 comꢀ
plexes of these crownophanes with paraquat 9•2PF6
(Table 2). Such a spectral pattern is characteristic of most
catenanes and pseudorotaxanes, indicating the formation
of sufficiently stable 1 : 1 complexes of these crownophanes
with paraquat 9•2PF6.32—34 The most intense peak of the
1 : 1 complex was observed for crownophane 1c with the
tetra(ethylene glycol) bridges between the aromatic fragꢀ
ments. For crownophane 1d, the peak was slightly less
intense. The mass spectrum of a complex of crownophane
1b contains a substantially weaker peak. No peak was
detected for a complex of crownophane 1a, in which the
aromatic fragments are linked by the diethylene glycol
bridges. Since the peak intensity ratio of complex ions of
similar ligands seems to correlate with the stabilities of
the complexes, one can believe that compound 1a forms
no complex with paraquat 9•2PF6 under the condiꢀ
tions of the FAB MS experiment, in contrast to larger
crownophanes 1b—d.
In the 1H NMR spectra of equimolar mixtures of
crownophanes 1b—d with paraquat 9•2PF6, the signals
a
Ha
Hc
H(4), H(8)
H(2), H(6)
Hb
H(3), H(7)
b
c
Hα
Hβ
8.5
8.0
7.5
7.0
δ
1
Fig. 1. Fragments of the H NMR spectra of crownophane 1c (a), its equimolar mixture with paraquat 9•2PF6 (b), and paraquat
9•2PF6 (c) in CD3CN—CDCl3 (4 : 3).

Crownophanes with fluorenone and naphthalene
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
989
Table 2. FAB MS data for mixtures of crownophanes 1a—d with
paraquat 9•2PF6
A
a
0.8
0.7
Compound
[M]+ b
[M – PF6]+ [Mcrown + H]+ c
a
0.6
0.5
0.4
0.3
0.2
0.1
1a
1b
1c
1d
[988]
[1076]
[1164]
[1252]
—
931 (4)
1019 (21)
1107 (18)
513
601
689
777
1a
1b
1c
1d
a The relative intensities (%) of the corresponding peaks are
given in parentheses.
b No molecular ion peaks of the complexes were observed.
c The peaks of the protonated crownophanes.
for all the aromatic protons in the crownophanes and
paraquat are shifted upfield compared to their positions in
the spectra of the individual compounds (Fig. 1). The
upfield shifts of the aromatic protons in the macrocyclic
host molecule and paraquat 9•2PF6 have been shown35,36
to be a reliable spectroscopic indication of the formation
of inclusion complexes of the pseudorotaxane type. The
shifts of the signals for the Hα and Hβ protons in paraquat
9•2PF6 for similar complexes are proportional, to a first
approximation, to their stabilities.
400
450
500
550
600
λ/nm
A
1c
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
b
1b
1d
The spectrum of an equimolar mixture of the smallest
crownophane 1a with paraquat 9•2PF6 is virtually identiꢀ
cal with the sum of the spectra of its components. Apparꢀ
ently, no inclusion complex is formed. With an extention
of the crownophane macrocycle, the upfield shifts of the
signals for the Hα and Hβ protons in paraquat 9•2PF6
and, probably, the stabilities of the resulting complexes
increase. According to the ∆δ values obtained for these
protons, crownophane 1c should form the most stable
inclusion complex with paraquat 9•2PF6 (Table 3). In
1a
400
450
500
550
600
λ/nm
Fig. 2. Electronic absorption spectra of solutions of crownꢀ
ophanes 1a—d (1.5•10–5 mol L–1) (a) and their mixtures with
paraquat 9•2PF6 (7 equiv.) (b).
1
general, the H NMR data on the stabilities of the comꢀ
plexes of crownophanes 1a—d with paraquat 9•2PF6 agree
well with the FAB MS data.
pounds, which is characteristic of pseudorotaxanes,
rotaxanes, and catenanes.33 Simultaneously, the visible
region of the spectra contains an additional band superꢀ
imposed on the absorption band of the carbonyl group of
fluorenone. Apparently, this band is due to the formation
of pseudorotaxane complexes stabilized by chargeꢀtransꢀ
fer donor—acceptor interactions of the πꢀdonating aroꢀ
matic subunits of the cyclophanes with the πꢀwithdrawing
On addition of a solution of paraquat 9•2PF6 to soluꢀ
tions of crownophanes 1b—d in acetonitrile, the initial
orange solutions turned dark red. This was accompanied
by substantial changes in both the visible and UV regions
of the electronic absorption spectra of these systems. The
intensities of the bands in the UV region decrease comꢀ
pared to the sum of the spectra of the individual comꢀ
Table 3. The upfield shifts ∆δ of the signals for the aromatic protons of crownophanes 1a—d in the 1H NMR spectra
of their equimolar mixtures with paraquat 9•2PF6
Compound
–∆δ
Ha
Hb
Hc
H(2), H(6)
H(3), H(7)
H(4), H(8)
Hα
Hβ
1a
1b
1c
1d
0
0.01
0.06
0.08
0.02
0
0
0
0.01
0
0.01
0.17
0.20
0.13
0.01
0.14
0.27
0.15
0.02
0.49
0.55
0.30
0.17
0.23
0.09
0.02
0.05
0
0.04
0.04
0.03
0.04

990
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Lukyanenko et al.
was 29.3 g (77%), red crystals, m.p. 91—92 °C. Found (%):
C, 62.82; H, 6.65. C25H32O9. Calculated (%): C, 63.01; H, 6.77.
bipyridinium fragments of paraquat 9•2PF6, which is in
the cavity of the macrocycle.32,33,36 With an increase in
the molar crownophane : paraquat ratio, this band beꢀ
comes more intense and its maximum experiences a slight
bathochromic shift. The largest relative change in the
intensity of this band was observed for a complex of
crownophane 1c with paraquat 9•2PF6. The electronic
absorption spectra in case of the smallest crownophane 1a
show no changes. Obviously, in this case, no pseudoꢀ
rotaxane is formed or the resulting complex have no doꢀ
nor—acceptor interactions between the aromatic fragꢀ
ments of the crownophane and paraquat (Fig. 2).
In conclusion, note that the formation of pseudoꢀ
rotaxanes in the reactions of paraquat 9•2PF6 with
crownophanes 1b—d make the latter promising for use in
the synthesis of supramolecular structures of the rotaxane
and catenane types.
UV (MeOH), λmax/nm (logε): 270 (4.95), 473 (2.53). IR, ν/cm–1
:
1
1700 (C=O). H NMR, δ: 2.18 (br.s, 2 H, OH); 3.63 (t, 4 H,
CH2O, J = 4.2 Hz); 3.68—3.82 (m, 12 H, CH2O); 3.87, 4.17
(both t, 4 H each, CH2O, J = 4.5 Hz); 6.98 (dd, 2 H, Hb, J =
8.1 Hz, J = 2.2 Hz); 7.17 (d, 2 H, Ha, J = 2.2 Hz); 7.28 (d, 2 H,
Hc, J = 8.1 Hz). MS (EI), m/z (Irel (%)): 476 [M]+ (41), 432 (3),
344 (3), 212 (11), 89 (26), 45 (100).
2,7ꢀBis(12ꢀhydroxyꢀ1,4,7,10ꢀtetraoxadodecyl)ꢀ9Hꢀfluorenꢀ
9ꢀone (4c) was purified by recrystallization from ethanol—ether
(1 : 3). The yield was 36.1 g (80%), a finely crystalline orange
solid, m.p. 61—63 °C. Found (%): C, 61.87; H, 6.94. C29H40O11.
Calculated (%): C, 61.69; H, 7.14. UV (MeOH), λmax/nm (logε):
270 (4.89), 300 (3.83), 312 (3.80), 469 (2.47). IR, ν/cm–1
:
1
1700 (C=O). H NMR, δ: 2.07 (br.s, 2 H, OH); 3.61 (t, 4 H,
CH2O, J = 4.5 Hz); 3.65—3.77 (m, 20 H, CH2O); 4.17, 4.28
(both t, 4 H each, CH2O, J = 4.7 Hz); 6.97 (dd, 2 H, Hb, J =
8.1 Hz, J = 2.5 Hz); 7.17 (d, 2 H, Ha, J = 2.5 Hz); 7.28 (d, 2 H,
Hc, J = 8.1 Hz). MS (EI), m/z (Irel (%)): 564 [M]+ (14), 388 (2),
212 (10), 89 (18), 45 (100).
Experimental
2,7ꢀBis(15ꢀhydroxyꢀ1,4,7,10,13ꢀpentaoxapentadecyl)ꢀ9Hꢀ
fluorenꢀ9ꢀone (4d). A solution of KOH (12 g, 0.215 mol) in
anhydrous EtOH (30 mL) was added to a suspension of comꢀ
pound 2 (21.2 g, 0.1 mol) and NaI (1 g) in anhydrous EtOH
(150 mL). The mixture was stirred at 40 °C for 15 min and
chlorohydrin 3d (61.6 g, 0.24 mol) was added. The reaction
mixture was refluxed for 50 h. The solvent was removed under
reduced pressure, the residue was dissolved in water (200 mL),
and the product was extracted with CHCl3 (700 mL). The exꢀ
tract was filtered and washed with 5% NaOH until the aqueous
layer stopped becoming colored (~6—7 times), 1% HCl, and
brine. The organic phase was dried over MgSO4, filtered through
a column with Al2O3, and concentrated under reduced pressure.
Column chromatography (SiO2, CHCl3—MeOH (100 : 5)) gave
diol 4d as a dark red oil that crystallized with time. The yield was
52.2 g (80%). Found (%): C, 60.72; H, 7.41. C33H48O13. Calcuꢀ
lated (%): C, 60.57; H, 7.35. UV (MeOH), λmax/nm (logε): 270
(4.92), 300 (3.84), 312 (3.82), 465 (2.59). IR, ν/cm–1: 1700
(C=O). 1H NMR, δ: 2.82 (br.s, 2 H, OH); 3.57—3.77 (m, 32 H,
CH2O); 3.86, 4.15 (both t, 4 H each, CH2O, J = 4.7 Hz); 6.96
(dd, 2 H, Hb, J = 8.1 Hz, J = 2.5 Hz); 7.15 (d, 2 H, Ha, J =
2.5 Hz); 7.27 (d, 2 H, Hc, J = 8.1 Hz). MS (EI), m/z (Irel (%)):
652 [M]+ (7), 212 (10), 89 (21), 45 (100).
Synthesis of ditosylates 5a—d (general procedure). A soluꢀ
tion of pꢀtoluenesulfonyl chloride (14.3 g, 0.075 mol) in dry
dioxane (30 mL) was added dropwise at 0—5 °C for 2 h to a
solution of diol 4a—d (0.03 mol) and Et3N (12.6 mL, 0.09 mol)
in CHCl3 (120 mL). The reaction mixture was warmed to ~20 °C
and stirred at this temperature for 30 h. Then an equal volume of
CHCl3 was added. The resulting solution was successively washed
with aqueous 5% HCl, aqueous 10% NH3, water, and brine,
dried over anhydrous MgSO4, and concentrated under reduced
pressure. The residue was dissolved in boiling propanꢀ2ꢀol and
cooled. Crystalline ditosylates were washed with EtOH; oils
were suspended several times in warm EtOH and the EtOH was
decanted. The product was dissolved in benzene, concentrated
under reduced pressure, and dried in vacuo.
1
H and 13C NMR spectra were recorded on a Varian
VXRꢀ300 instrument (300 and 75.5 MHz, respectively)
in CDCl3. 1H NMR spectra of complexes were recorded in
CDCl3—CD3CN (3 : 4, v/v). Mass spectra (EI) were recorded
on an MXꢀ1321 mass spectrometer (direct inlet probe, 70 eV).
FAB mass spectra were recorded on a VG 7070EQ mass specꢀ
trometer (Xe, 8 kV) in the 3ꢀnitrobenzyl alcohol matrix.
IR spectra were recorded on a Specord IRꢀ75 spectrophotomꢀ
eter (KBr pellets). UV spectra were recorded on a Specord Mꢀ40
spectrophotometer. Preparative column chromatography was
carried out on Kieselgel 60 silica gel (0.063—0.100 mm, Merck).
The purity of all the compounds obtained was checked by TLC
(Sorbfil UFꢀ254). Melting points were measured in open capilꢀ
laries and are given uncorrected. Compounds 2,23 7,37 and
38
9•2PF6 were prepared as described earlier.
Synthesis of diols 4a—c (general procedure). 2,7ꢀDihydroxyꢀ
fluorenone 2 (16.96 g, 0.08 mol) was added under argon to a
suspension of freshly calcined K2CO3 (66.2 g, 0.48 mol) and
NaI (24 g, 0.16 mol) in dry DMF (400 mL). The mixture was
stirred at 80 °C for 1 h and chlorohydrin 3a—c (0.24 mol) was
added. The reaction mixture was heated for an additional 35 h
and filtered. The filtrate was evaporated to dryness in vacuo. The
residue was dissolved in chloroform and the resulting solution
was washed with aqueous 5% NaOH and twice with water, dried
over anhydrous MgSO4, and concentrated in vacuo. The residue
was purified as specified below.
2,7ꢀBis(6ꢀhydroxyꢀ1,4ꢀdioxahexyl)ꢀ9Hꢀfluorenꢀ9ꢀone (4a)
was purified by recrystallization from propanꢀ2ꢀol. The yield
was 24.2 g (78%), red crystals, m.p. 117—119 °C. Found (%):
C, 65.19; H, 6.29. C21H24O7. Calculated (%): C, 64.94; H, 6.23.
UV (MeOH), λmax/nm (logε): 270 (5.01), 469 (2.43). IR, ν/cm–1
:
1700 (C=O). 1H NMR, δ: 1.97 (br.s, 2 H, OH); 3.65—3.72,
3.74—3.82, 3.84—3.92, 4.14—4.21 (all m, 4 H each, CH2O);
6.97 (dd, 2 H, Hb, J = 8.1 Hz, J = 2.5 Hz); 7.17 (d, 2 H, Ha, J =
2.2 Hz); 7.29 (d, 2 H, Hc, J = 8.1 Hz). MS (EI), m/z (Irel (%)):
388 [M]+ (44), 300 (7), 212 (35), 89 (8), 45 (100).
2,7ꢀBis(6ꢀtosyloxyꢀ1,4ꢀdioxahexyl)ꢀ9Hꢀfluorenꢀ9ꢀone (5a).
The yield was 18.4 g (88%), orange crystals, m.p. 109—112 °C.
Found (%): C, 60.47; H, 5.41. C35H36O11S2. Calculated (%):
2,7ꢀBis(9ꢀhydroxyꢀ1,4,7ꢀtrioxanonyl)ꢀ9Hꢀfluorenꢀ9ꢀone (4b)
was purified by recrystallization from propanꢀ2ꢀol. The yield

Crownophanes with fluorenone and naphthalene
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
991
C, 60.33; H, 5.21. UV (C4H8O2), λmax/nm (logε): 272 (4.96),
301 (3.90), 314 (3.88), 464 (2.57). IR, ν/cm–1: 1700 (C=O).
1H NMR, δ: 2.42 (s, 6 H, Me); 3.73—3.83 (m, 8 H, CH2O); 4.07
(t, 4 H, CH2O, J = 4.5 Hz); 4.21 (t, 4 H, CH2O, J = 4.8 Hz);
6.95 (dd, 2 H, Hb, J = 8.1 Hz, J = 2.2 Hz); 7.12 (d, 2 H, Ha, J =
2.2 Hz); 7.27—7.36 (m, 6 H, HAr, Hc); 7.80 (d, 4 H, HAr, J =
8.1 Hz). MS (FAB), m/z (Irel (%)): 697 [M + H]+ (100), 542
[M – Ts + H]+ (51).
C, 72.64; H, 5.51. UV (MeCN), λmax/nm (logε): 227 (4.68), 271
(4.76), 298 (4.16), 312 (4.05), 324 (3.83), 472 (2.38). IR, ν/cm–1
:
1700 (C=O). 1H NMR, δ: 3.93—3.99 (m, 4 H, CH2O);
4.01—4.13 (m, 8 H, CH2O); 4.34 (t, 4 H, CH2O, J = 4.2 Hz);
6.48 (d, 2 H, H(2), H(6), J = 7.8 Hz); 6.81 (dd, 2 H, Hb, J =
8.1 Hz, J = 2.2 Hz); 6.86—6.92 (m, 4 H, Hc, Ha); 7.06 (t, 2 H,
H(3), H(7), J = 8.1 Hz); 7.34 (d, 2 H, H(4), H(8), J = 8.4 Hz).
13C NMR, δ: 67.5, 69.0, 69.4, 69.8, 104.5, 111.4, 113.9, 119.7,
121.4, 124.7, 126.0, 135.2, 137.2, 153.7, 157.9, 192.1. MS (EI),
m/z (Irel (%)): 512 [M]+ (100), 256 (10), 211 (5), 160 (8), 45 (7).
2,5,8,11,13,16,19,22ꢀoctaoxaꢀ1(2,7)ꢀfluorenaꢀ12(5,1)ꢀ
naphthalenacyclodocosaphanꢀ19ꢀone (1b). The yield was 1.17 g
(20%), reddish orange scaly crystals, m.p. 152—153 °C (from
EtOH). Found (%): C, 69.76; H, 5.97. C35H36O9. Calcuꢀ
lated (%): C, 69.99; H, 6.04. UV (MeCN), λmax/nm (logε): 226
(4.80), 271 (4.87), 295 (4.16), 312 (4.07), 326 (3.82), 474 (2.34).
IR, ν/cm–1: 1700 (C=O). 1H NMR, δ: 3.78 (br.s, 8 H, CH2O);
3.85—3.94 (m, 8 H, CH2O); 4.06 (t, 4 H, CH2O, J = 5.3 Hz);
4.13—4.18 (m, 4 H, CH2O); 6.57 (d, 2 H, H(2), H(6), J =
7.5 Hz); 6.81 (d, 2 H, Hc, J = 8.1 Hz); 6.85 (dd, 2 H, Hb, J =
8.1 Hz, J = 2.2 Hz); 6.92 (d, 2 H, Ha, J = 1.9 Hz); 7.08 (t, 2 H,
H(3), H(7), J = 8.1 Hz); 7.58 (d, 2 H, H(4), H(8), J = 8.4 Hz).
13C NMR, δ: 67.4, 68.2, 69.6, 69.9, 71.1, 105.2, 110.6, 114.3,
120.0, 121.0, 124.7, 126.4, 135.5, 137.2, 154.0, 158.9, 193.0.
MS (EI), m/z (Irel (%)): 600 [M]+ (100), 300 (7), 212 (2), 160 (5).
2,5,8,11,14,16,19,22,25,28ꢀDecaoxaꢀ1(2,7)ꢀfluorenaꢀ
15(5,1)ꢀnaphthalenacyclooctacosaphanꢀ19ꢀone (1c). The yield
was 1.31 g (19%), red scaly crystals, m.p. 118.5—119.5 °C (from
EtOH). Found (%): C, 68.13; H, 6.21. C39H44O11. Calcuꢀ
lated (%): C, 68.01; H, 6.44. UV (MeCN), λmax/nm (logε): 226
(4.79), 271 (4.87), 296 (4.17), 312 (4.08), 326 (3.84), 472 (2.43).
2,7ꢀBis(9ꢀtosyloxyꢀ1,4,7ꢀtrioxanonyl)ꢀ9Hꢀfluorenꢀ9ꢀone
(5b). The yield was 19.7 g (84%), a dark red oil that crystallized
under a layer of hexane, m.p. 68—70 °C. Found (%): C, 59.56;
H, 5.47. C39H44O13S2. Calculated (%): C, 59.68; H, 5.65.
UV (C4H8O2), λmax/nm (logε): 225 (4.72), 272 (5.14), 301 (4.10),
1
314 (4.08), 469 (2.71). IR, ν/cm–1: 1700 (C=O). H NMR, δ:
2.43 (s, 6 H, Me); 3.57—3.75 (m, 12 H, CH2O); 3.79—3.87 (m,
4 H, CH2O); 4.08—4.21 (m, 8 H, CH2O); 6.97 (dd, 2 H, Hb,
J = 8.1 Hz, J = 2.5 Hz); 7.15 (d, 2 H, Ha, J = 2.5 Hz); 7.29 (d,
2 H, Hc, J = 8.1 Hz); 7.33, 7.80 (both d, 4 H each, HAr, J =
8.3 Hz). MS (FAB), m/z (Irel (%)): 784 [M]+ (100), 630
[M – Ts + H]+ (12).
2,7ꢀBis(12ꢀtosyloxyꢀ1,4,7,10ꢀtetraoxadodecyl)ꢀ9Hꢀfluorenꢀ
9ꢀone (5c). The yield was 23.1 g (80%), a dark red oily subꢀ
stance. Found (%): C, 58.98; H, 5.83. C43H52O15S2. Calcuꢀ
lated (%): C, 59.16; H, 6.00. UV (C4H8O2), λmax/nm (logε): 229
(4.40), 272 (4.96), 302 (3.88), 314 (3.87), 464 (2.64). IR, ν/cm–1
:
1700 (C=O). 1H NMR, δ: 2.43 (s, 6 H, Me); 3.60 (s, 8 H,
CH2O); 3.62—3.76 (m, 12 H, CH2O); 3.85 (t, 4 H, CH2O, J =
4.7 Hz); 4.11—4.20 (m, 8 H, CH2O); 6.97 (dd, 2 H, Hb, J =
8.1 Hz, J = 2.2 Hz); 7.15 (d, 2 H, Ha, J = 2.2 Hz); 7.28 (d, 2 H,
Hc, J = 8.1 Hz); 7.33, 7.79 (both d, 4 H each, HAr, J = 8.1 Hz).
MS (FAB), m/z (Irel (%)): 895 [M + Na]+ (3), 872 [M]+ (100),
718 [M – Ts – H]+ (14).
1
IR, ν/cm–1: 1700 (C=O). H NMR, δ: 3.68—3.79 (m, 16 H,
2,7ꢀBis(15ꢀtosyloxyꢀ1,4,7,10,13ꢀpentaoxapentadecyl)ꢀ9Hꢀ
fluorenꢀ9ꢀone (5d). The yield was 18.3 g (70%), a dark red oily
substance. Found (%): C, 58.89; H, 6.29. C47H60O17S2. Calcuꢀ
lated (%): C, 58.74; H, 6.29. UV (C4H8O2), λmax/nm (logε): 226
CH2O); 3.81—3.88 (m, 4 H, CH2O); 3.29 (t, 4 H, CH2O, J =
4.9 Hz); 4.03—4.13 (m, 8 H, CH2O); 6.63 (d, 2 H, H(2), H(6),
J = 7.5 Hz); 6.83 (dd, 2 H, Hb, J = 8.1 Hz, J = 2.2 Hz); 6.94 (d,
2 H, Hc, J = 8.1 Hz); 7.01 (d, 2 H, Ha, J = 1.9 Hz); 7.16 (t, 2 H,
H(3), H(7), J = 8.1 Hz); 7.71 (d, 2 H, H(4), H(8), J = 8.4 Hz).
13C NMR, δ: 67.7, 68.2, 69.6, 69.7, 70.8, 70.9, 71.0, 105.4,
110.4, 114.4, 120.3, 121.0, 124.9, 126.6, 135.7, 137.4, 154.2,
159.1, 193.2. MS (EI), m/z (Irel (%)): 688 [M]+ (100), 344 (7),
211 (6), 160 (6), 45 (32).
2,5,8,11,14,17,19,22,25,28,31,34ꢀDodecaoxaꢀ1(2,7)ꢀ
fluorenaꢀ18(5,1)ꢀnaphthalenacyclotetratriacontaphanꢀ19ꢀone
(1d). The yield was 1.74 g (21%), an orange powder, m.p.
111—112 °C (from MeOH). Found (%): C, 66.61; H, 6.87.
C43H52O13. Calculated (%): C, 66.48; H, 6.75. UV (MeCN),
(4.45), 272 (4.59), 302 (3.88), 314 (3.86), 465 (2.41). IR, ν/cm–1
:
1700 (C=O). 1H NMR, δ: 2.44 (s, 6 H, Me); 3.58 (s, 8 H,
CH2O); 3.60—3.76 (m, 20 H, CH2O); 3.86 (t, 4 H, CH2O, J =
4.7 Hz); 4.16 (t, 8 H, CH2O, J = 4.7 Hz); 6.97 (dd, 2 H, Hb, J =
8.1 Hz, J = 2.2 Hz); 7.15 (d, 2 H, Ha, J = 2.2 Hz); 7.28 (d, 2 H,
Hc, J = 8.1 Hz); 7.33, 7.80 (both d, 4 H each, HAr, J = 8.1 Hz).
MS (FAB), m/z (Irel (%)): 999 [M + K]+ (3), 983 [M + Na]+
(18), 960 [M]+ (100), 806 [M – Ts + H]+ (6).
Synthesis of fluorenoneꢀcontaining crownophanes 1a—d (genꢀ
eral procedure). A solution of 1,5ꢀdihydroxynaphthalene (1.6 g,
0.01 mol) and ditosylate 5a—d (0.01 mol) in anhydrous DMF
(400 mL) was added dropwise for 10 h to a stirred suspension of
dry K2CO3 (5.52 g, 0.04 mol) in anhydrous DMF (600 mL). The
reaction temperature was maintained at 80 °C. After the addiꢀ
tion was completed, the mixture was stirred at this temperature
for an additional 40 h, cooled, filtered, and concentrated in vacuo.
The residue was dissolved in CHCl3 (300 mL). The resultꢀ
ing solution was filtered, successively washed with 5% HCl,
5% NaOH, and brine, dried over MgSO4, and concentrated
in vacuo. The product was purified by column chromatography
(SiO2, CHCl3—MeOH (100 : 2)) and recrystallized.
λ
max/nm (logε): 225 (4.85), 271 (4.92), 296 (4.23), 313 (4.17),
326 (3.91), 472 (2.50). IR, ν/cm–1: 1700 (C=O). H NMR, δ:
3.62—3.79 (m, 24 H, CH2O); 3.82 (t, 4 H, CH2O, J = 4.5 Hz);
3.93 (t, 4 H, CH2O, J = 4.8 Hz); 4.07 (t, 4 H, CH2O, J =
4.5 Hz); 4.15 (t, 4 H, CH2O, J = 4.8 Hz); 6.68 (d, 2 H, H(2),
H(6), J = 7.5 Hz); 6.84 (dd, 2 H, Hb, J = 8.1 Hz, J = 2.2 Hz);
7.00—7.07 (m, 4 H, Hc, Ha); 7.23 (t, 2 H, H(3), H(7), J =
8.1 Hz); 7.74 (d, 2 H, H(4), H(8), J = 8.4 Hz). 13C NMR, δ:
67.7, 68.0, 69.6, 69.7, 70.7, 70.8, 70.8, 71.0, 71.0, 105.4, 110.2,
114.5, 120.4, 120.9, 125.0, 126.6, 135.7, 137.4, 154.2, 159.1,
193.4. MS (EI), m/z (Irel (%)): 776 [M]+ (100), 388 (3), 211 (8),
160 (6), 45 (93).
1
2,5,8,10,13,16ꢀHexaoxaꢀ1(2,7)ꢀfluorenaꢀ9(5,1)ꢀnaphthaꢀ
lenacyclohexadecaphanꢀ19ꢀone (1a). The yield was 0.46 g (9%),
a yellowish orange powder, m.p. 202—202.5 °C (from butanꢀ
1ꢀol). Found (%): C, 72.84; H, 5.62. C31H28O7. Calculated (%):
1,5ꢀDimethoxynaphthalene (8). A solution of NaOH (2.64 g,
0.066 mol) in water (24 mL) was added for 20 min to a mixture
of 1,5ꢀdihydroxynaphthalene (4.8 g, 0.03 mol) and dimethyl

992
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Lukyanenko et al.
sulfate (7.9 g, 0.063 mol) in water (25 mL). The addition rate
was regulated so as to prevent the temperature from increasing
above 30 °C. The reaction mixture was stirred for 45 min and
then at 70 °C for an additional 2 h. After cooling, the precipiꢀ
tate was filtered off, dried, and recrystallized from heptane
with Al2O3. The yield was 1.9 g (34%), m.p. 183—184 °C
(cf. Ref. 39: 183—184 °C). Found (%): C, 76.81; H, 6.71.
C12H12O2. Calculated (%): C, 76.57; H, 6.43. 1H NMR
(CDCl3), δ: 3.97 (s, 6 H, Me); 6.83 (d, 2 H, H(2), H(6), J =
7.47 Hz); 7.36 (t, 2 H, H(3), H(7), J = 8.09 Hz); 7.83 (d, 2 H,
H(4), H(8), J = 8.72 Hz). MS, m/z (Irel (%)): 188 [M]+ (100),
173 (55).
18. A. Yu. Lyapunov, T. I. Kirichenko, E. Yu. Kulygina, and
N. G. Lukyanenko, Zh. Org. Khim., 2005, 41, 144 [Russ.
J. Org. Chem., 2005, 41, 144 (Engl. Transl.)].
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Received January 19, 2007