Synthesis of Polyfluorinated Tetraoxacalix[4]arenes by Reaction of Pentafluoronitrobenzene with Resorcinol, Orcinol, and Tetrafluororesorcinol

Article abstract of DOI:10.1134/S1070428020070052

Abstract: Successive reactions of pentafluoronitrobenzene with resorcinol, orcinol, andtetrafluororesorcinol in acetonitrile in the presence of triethylamine affordedpolyfluorinated ABAB and ABAC tetraoxacalix[4]arenes. Analysis of the¹H and

Full text of DOI:10.1134/S1070428020070052

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 7, pp. 1153–1159. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 7, pp. 1030–1038.
Synthesis of Polyfluorinated Tetraoxacalix[4]arenes
by Reaction of Pentafluoronitrobenzene with Resorcinol,
Orcinol, and Tetrafluororesorcinol
V. N. Kovtonyuka,*, H. Hana,b, and Yu. V. Gatilova
a Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
b Novosibirsk National Research State University, Novosibirsk, 630090 Russia
*e-mail: kovtonuk@nioch.nsc.ru
Received February 28, 2020; revised March 27, 2020; accepted April 13, 2020
Abstract—Successive reactions of pentafluoronitrobenzene with resorcinol, orcinol, and tetrafluororesorcinol
in acetonitrile in the presence of triethylamine afforded polyfluorinated ABAB and ABAC tetraoxacalix[4]-
arenes. Analysis of the 1H and 19F NMR spectra of the synthesized oxacalixarenes indicated high conformational
mobility of the resorcinol and tetrafluororesorcinol fragments of their molecules due to interaction with the
solvent.
Keywords: polyfluorinated tetraoxacalixarenes, pentafluoronitrobenzene, resorcinol, orcinol, tetrafluoro-
resorcinol, conformational behavior
DOI: 10.1134/S1070428020070052
Tetraoxacalixarenes are among scaffolds used in
supramolecular chemistry to study host–guest inter-
molecular interactions [1]. A number of chemosensors
for neutral organic compounds [2–4], cations [5–7],
and anions [8–11] have been obtained on the basis of
tetraoxacalixarenes. The possibility of using oxacalix-
arenes as ion pair transporters through cell membranes
has been demonstrated [12–15]. Some oxacalixarenes
have been found to exhibit physiological activity [16].
Likewise, successive reactions of pentafluoronitroben-
zene with resorcinol and tetrafluororesorcinol in aceto-
nitrile in the presence of triethylamine gave triphenyl
ethers 1a and 3a and tetraoxacalixarenes 4a–8a
containing an impurity of the corresponding isomers
(Scheme 1). Diether 3a was synthesized previously in
a moderate yield (37%) by heating pentafluoronitro-
benzene with tetrafluororesorcinol in acetonitrile in the
presence of potassium carbonate [23].
Fluorinated tetraoxacalixarenes were synthesized
previously via [3+1] two-step fragment coupling ap-
proach by reaction of 4-substituted tetrafluoropyridines
with resorcinol and orcinol [17, 18], as well as by
reaction of dichlorotriazines with perfluorinated
dihydroxybenzenes [19].
The synthesis of tetraoxacalixarenes 4a–8a can be
performed both with intermediate isolation of triphenyl
ethers 1a, 1b, 3a, and 3b and via reaction of orcinol
with 2 equiv of pentafluoronitrobenzene under mild
conditions, followed by heating of the resulting mixture
of triphenyl ethers 2a and 2b with 1 equiv of orcinol or
tetrafluororesorcinol.
In this work we examined a fragment coupling
approach to the synthesis of polyfluorinated tetraoxa-
calixarenes via reaction of pentafluoronitrobenzene
with resorcinol, orcinol, and tetrafluororesorcinol. This
approach has been utilized by us in the synthesis of
A3B perfluorinated tetraoxacalixarenes [20]. Recently,
we have also shown that polyfluorinated ABAC tetra-
oxacalixarenes can be obtained by successively react-
ing perfluorinated m-xylene and pentafluorobenzoni-
trile with resorcinol and tetrafluororesorcinol [21, 22].
The structure of polyfluorinated tetraoxacalixarenes
4–8 was determined on the basis of spectral and ana-
1
lytical data. It was previously shown that the H and
19F NMR spectra of polyfluorinated tetraoxacalixarenes
are characterized by a significant upfield shift of the
1H and 19F signals of the lower rim atoms of the resor-
cinol fragments due to shielding by the neighboring
aromatic rings [20–22]. In the 1H and 19F NMR spectra
of 4–8 we also observed upfield shifts of the 25-H and
1153

KOVTONYUK et al.
1154
F
F
F
F
F
F
NO2
O
F
NO2
F
F
NO2
F
F
O
O
O
O
O
F
F
F
F
F F
F F
F
F
A
B
C
Fig. 1. Possible conformations of tetraoxacalixarene 5a in CDCl3 and (CD3)2CO solutions.
27-F signals. Here, the signal of 2-H located between
two 4-O2NC6F4O fragments of 1a can be used as refer-
ence in the 1H NMR spectrum. However, the magnitude
of the observed upfield shift depends on the solvent. In
and (CD3)2CO solutions adopt different equilibrium
conformations characterized by different degrees of
magnetic shielding of the lower-rim protons and
fluorines of the resorcinol fragments by the neighboring
aromatic rings. The limiting cases of this shielding are
illustrated by conformers A–C in Fig. 1. It should be
noted that the position of the lower-rim 26-F and 28-F
signals of the nitrobenzene fragments in the 19F NMR
spectra almost does not depend on the solvent.
A similar solvent dependence was observed for the
1
the H NMR spectra of 1a and 5a in CDCl3, the
difference between the chemical shifts of 2-H in 1a and
25-H in 5a is 0.96 ppm, whereas the corresponding
difference in the spectra recorded in acetone-d6 is
0.42 ppm. Likewise, the 27-F chemical shift of 5a also
strongly depends on the solvent and is δF 7.1 ppm in
CDCl3 and 11.5 ppm in acetone-d6. The signal of 2-F
(located between the aryloxy groups) in the 19F NMR
spectra of perfluorinated triphenyl ethers is observed at
δF ~11–14 ppm, and its position weakly depends on the
solvent (cf. [21] and the data for ethers 3a and 3b).
Presumably, tetraoxacalixarene 5a molecules in CDCl3
1
25-H and 27-H signals in the H NMR spectra of 6a.
Apart from the steric factor (conformation), variation
of the chemical shifts may be related to electronic
effects arising from conjugation between the lone elec-
tron pairs on the bridging oxygen atoms and aromatic
rings.
Scheme 1.
OH
Y
NO2
NO2
F
X
OH
O
O
O
O
NEt3, MeCN, 0–20°C
F
F
F
F
Y
X
+
Y
X
O2N
O2N
NO2
1a: X = Y = H
2a: X = Me, Y = H
3a: X = Y = F
82% (86:14)
64% (96:4)
1b: X = Y = H
2b: X = Me, Y = H
3b: X = Y = F
OH
A
NO2
O2N
O
F
F
F
O
O
O
Z
OH
NEt3, MeCN, 80°C
A
+
A
Z
Z
X
X
Y
Y
O
O
O
O
F
NO2
NO2
4a: X = Y = Z = A = H
62% (86:14)
46% (86:14)
61% (86:14)
44% (80:20)
38% (93:7)
4b: X = Y = Z = A = H
5a: X = Y = H, Z = A = F
6a: X = Z = Me, Y = A = H
7a: X = Me, Y = H, Z = A = F
8a: X = Y = F, Z = A = H
5b: X = Y = H, Z = A = F
6b: X = Z = Me, Y = A = H
7b: X = Me, Y = H, Z = A = F
5b: X = Y = F, Z = A = H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

SYNTHESIS OF POLYFLUORINATED TETRAOXACALIX[4]ARENES
1155
Table 1. Chemical shifts (δ, δF, ppm) of some nuclei in the 1H and 19F NMR spectra of triphenyl ether 1a and tetraoxacalixarene
5a in different solvents
Solvent
Carbon tetrachloride
Chloroform
2-H (1a)
6.83
25-H (5a)
5.96
Δδ(2-H1a – 25-H5a)
27-F (5a)
6.6
0.87
0.91
0.91
0.95
6.84
5.93
7.1
Methylene chloride
Benzyl chloride
Chlorobenzene
Toluene
6.84
5.93
8.2
6.71
5.76
8.1
5.88
8.0
5.74
8.5
Diethyl ether
Nitrobenzene
Acetone
7.06
7.06
7.21
6.97
6.23
0.83
0.68
0.36
0.68
9.3
6.38
9.2
6.85
11.4
11.6
Acetonitrile
6.29
The H and 19F NMR spectra of triphenyl ether 1a
and tetraoxacalixarenes 5a were also recorded in other
solvents (Table 1). The results showed that the solvents
used can be arbitrarily divided into three groups. The
first group of solvents includes chloroform and carbon
tetrachloride, where the NMR spectra of 5a displayed
a significant upfield shift of both 25-H (resorcinol) and
27-F (tetrafluororesorcinol) signals. This may be due to
the existence of molecule 5a in these solvents as equi-
librium conformer A (Fig. 1). In going to acetone and
acetonitrile (second group), the magnitude of the up-
field shift of the 25-H and 27-F signals is significantly
lower, which suggests shift of the conformational
equilibrium toward structure B (Fig. 1). Solvents of
the third group (chlorobenzene, toluene, and benzyl
chloride) give rise to a significant upfield shift of the
25-H signal but a smaller shift of the 27-F signal,
presumably due to partial withdrawal of the
fluorine atom from the area shielded by the neighbor-
ing nitrobenzene fragments (conformer C in Fig. 1).
The above groups of solvents are likely to differ from
each other in the mode of interaction with tetraoxa-
calixarene 5a molecules. Aromatic solvents are charac-
terized by a substantial contribution of π–π interaction
with tetrafluorobenzene ring, whereas the interaction
of 5a with chloromethanes could involve mainly
insertion of the solvent molecules into the calixarene
cavity between the resorcinol and tetrafluororesorcinol
fragments. Various interaction modes, in particular π–π
interaction between tetraoxacalixarenes and aromatic
compounds, were previously discussed in [24].
The molecular structure of a crystalline 2:1 complex
of tetraoxacalixarene 5a with chlorobenzene was
studied by X-ray diffraction (Fig. 2). It was similar to
the structure of polyfluorinated tetraoxacalixarenes
described by us in [20–22]. The dihedral angle between
the opposite nitrobenzene rings is 40.4°, and the
dihedral angle between the other two rings is 74.5°.
Chlorobenzene molecule is involved in π–π stacking
interaction with the tetrafluorobenzene rings of the two
neighboring tetraoxacalixarene molecules 5a. The dis-
tance between the centroids of the tetrafluorobenzene
rings to the chlorobenzene ring plane is 3.49 Å, and the
intercentroid distances are 3.60 and 3.82 Å, respec-
tively. In addition, there are π–π interactions between
pairs of the nitrobenzene rings with disordered nitro
groups and benzene rings of the neighboring molecules
(intercentroid distances 3.86 and 3.74 Å; centroid–
1
Fig. 2. Molecular structure of tetraoxacalixarene 5a according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

KOVTONYUK et al.
1156
plane distances 3.42 and 3.47 Å). Unlike the
resorcinol fragment, π–π stacking interaction is likely
to partially force the tetrafluorobenzene ring out of the
overlap zone with the neighboring nitrobenzene
rings. The X-ray diffraction data for compound 5a are
consistent with its behavior in aromatic solvents
according to the NMR data.
31470 reflection intensities were measured in the range
1.5° < θ < 27.9°, including 6187 independent reflec-
tions (Rint = 0.0405) and 4400 reflections with I >
2σ(I); number of variables 441. Final divergence
factors: R1 = 0.0659 [reflections with I > 2σ(I)], wR2 =
0.2229 (all independent reflections); goodness of fit
S = 1.059. The coordinates of atoms and their thermal
displacement parameters were deposited to the
Cambridge Crystallographic Data Centre (CCDC entry
no. 1986975) [25].
EXPERIMENTAL
1
The 19F and H NMR spectra were recorded on
1,3-Bis(2,3,5,6-tetrafluoro-4-nitrophenoxy)-
benzene (1a) and 1,2,3,4-tetrafluoro-5-nitro-6-
[3-(2,3,5,6-tetrafluoro-4-nitrophenoxy)phenoxy]-
benzene (1b) (mixture of isomers). A solution of
0.22 g (2 mmol) of resorcinol and 0.85 g (4 mmol) of
pentafluoronitrobenzene in 15 mL of acetonitrile was
cooled to 0°C, a solution of 1.0 g (10 mmol) of
triethylamine in 5 mL of acetonitrile was added with
stirring, and the mixture was stirred for 2 h at 0°C and
for 1 h at room temperature. The solvent was distilled
off under reduced pressure (~20 mm Hg), and the
residue was subjected to silica gel column chromatog-
raphy using carbon tetrachloride–chloroform (~5:1 by
volume) as eluent. The product was 0.94 g (82%) of
a viscous material containing triphenyl ethers 1a and
1b at a ratio of 86:14 (according to the GC/MS data).
19F NMR spectrum, δF, ppm: in CDCl3: 1a: 11.7 m (4F,
o-F), 16.2 m (4F, m-F); 1b: 6.2 t (1F, 3-F, J = 21.0 Hz),
11.7 m (2F, 2′-F, 6′-F), 13.9 d.d (1F, 1-F, J = 20.0,
8.0 Hz), 14.5 t.d (1F, 2-F, J = 20.0, 4.0 Hz), 15.9 d.d.d
(1F, 4-F, J = 22.0, 8.0, 4.0 Hz), 16.1 m (2F, 3′-F, 5′-F);
in acetone-d6: 1a: 11.2 m (4F, o-F), 16.2 m (4F, m-F);
1b: 5.4 t (1F, 3-F), 11.2 m (2F, 2′-F, 6′-F), 13.4 d.d (1F,
1-F), 14.2 t.d (1F, 2-F), 15.8 d.d.d (1F, 4-F), 16.2 m
a Bruker AV-300 spectrometer at 282.36 MHz (relative
to C6F6 as internal standard) and 300 MHz, respec-
tively. The 13C NMR spectrum of 5a was measured
with a Bruker AV-400 spectrometer at 100.6 MHz. The
solvent effect on the 19F and 1H NMR spectra of 1a and
5a was studied using a coaxial insert (o.d. 4.1 mm)
made of tetrafluoroethylene–hexafluoropropylene co-
polymer, which was placed in a standard NMR ampule
filled with D2O; the chemical shifts were measured
relative to hexamethyldisiloxane (1H) and hexafluoro-
benzene (19F) as internal standards. The IR spectra
were recorded on a Bruker Vector 22 IR spectrometer.
The elemental compositions of polyfluorinated tetra-
oxacalix[4]arenes 4a–8a were determined by classical
methods, as well as from the high-resolution mass
spectra (electron impact, 70 eV) which were obtained
with a Termo Scientific DFS instrument. The progress
of reactions was monitored by TLC on silica gel 60
F254 plates (Merck). Silica gel with a particle size of
0.063–0.200 mm (Merck) was used for column chro-
matography.
The X-ray diffraction data for a single crystal of
5a·0.5(C6H5Cl) were obtained on a Bruker KAPPA
Apex II diffractometer (Mo Kα radiation, 296 K).
A correction for absorption was applied by SADABS
program. The structure was solved by the direct method
and was refined by the full-matrix least-squares method
in anisotropic approximation for non-hydrogen atoms.
The positions of hydrogen atoms were refined in
isotropic approximation according to the riding model.
All calculations were performed using SHELXTL and
SHELXL-2018/3 packages. One nitro group in mole-
cule 5a is disordered by two positions with a population
ratio of 0.638:0.362. The chlorobenzene solvate mole-
cule is located in the symmetry center and is disordered
by two positions with equal populations. Triclinic crys-
tal system; C24H4N2O8·0.5C6H5Cl, M 694.57; space
group P-1; unit cell parameters: a = 9.0585(3),
b = 11.1141(4), c = 14.4280(5) Å; α = 67.442(2),
β = 81.899(2), γ = 76.750(2)°; V = 1303.45(8) Å3;
Z = 2; dcalc = 1.770 g/cm3; μ = 0.225 mm–1. Total of
1
(2F, 3′-F, 5′-F). H NMR spectrum, δ, ppm: in CDCl3:
1a: 6.80 d.d (2H, 4-H, 6-H, J = 8.2, 2.2 Hz), 6.86 t (1H,
2-H, J = 2.2 Hz), 7.35 t (1H, 5-H, J = 8.2 Hz); 1b:
6.70–6.82 m (3H, 2-H, 4-H, 6-H), 7.32 t (1H, 5-H, J =
8.2 Hz); in acetone-d6: 1a: 7.13 d.d (2H, 4-H, 6-H),
7.28 t (1H, 2-H), 7.53 t (1H, 5-H); 1b: 7.00–7.21 m
(3H, 2-H, 4-H, 6-H), 7.50 t (1H, 5-H). Mass spectrum:
m/z 496 [M]+).
1,3-Bis(2,3,5,6-tetrafluoro-4-nitrophenoxy)-
2,4,5,6-tetrafluorobenzene (3a) and 1,2,4,5-tetra-
fluoro-3-nitro-6-[2,3,4,6-tetrafluoro-5-(2,3,4,5-tetra-
fluoro-6-nitrophenoxy)phenoxy]benzene (3b) (mix-
ture of isomers). A solution of 1.0 g (10 mmol) of tri-
ethylamine in 5 mL of acetonitrile was added with
stirring at room temperature to a solution of 0.36 g
(2 mmol) of tetrafluororesorcinol and 0.85 g (4 mmol)
pentafluoronitrobenzene in 15 mL acetonitrile. The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

SYNTHESIS OF POLYFLUORINATED TETRAOXACALIX[4]ARENES
1157
mixture was stirred for 4 h at room temperature and
was then refluxed for 4 h (80°C). The solvent was
distilled off under reduced pressure (~20 mm Hg), and
the residue was subjected to silica gel column
chromatography using carbon tetrachloride–chloroform
(~5:1 by volume) as eluent. The product was 0.65 g
(57%) of a viscous material containing triphenyl ethers
F 20.13; N 4.95. M 566. 19F NMR spectrum of 4b
(CCl4–CDCl3), δF, ppm (from the spectrum of mixture
4a/4b): 11.8 d (2F, 4-F, 16-F, J = 23.0 Hz), 16.9 d.d
(2F, 5-F, 17-F, J = 23.0, 10.0 Hz), 25.0 d (2F, 26-F,
28-F, J = 10.0 Hz).
4,5,10,11,12,17,18,26,27,28-Decafluoro-6,16-
d i n i t r o - 2 , 8 , 1 4 , 2 0 - t e t r a o x a p e n t a c y c l o -
[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,
9(27),10,12,15(26),16,18,21,23-dodecaene (5a),
4,5,10,11,12,16,17,26,27,28-decafluoro-6,18-dinitro-
2,8,14,20-tetraoxapentacyclo[19.3.1.13,7.19,13.115,19]-
octacosa-1(25),3(28),4,6,9(27),10,12,15(26),16,18,
21,23-dodecaene (5b), and 5,6,10,11,12,16,17,26,
27,28-decafluoro-4,18-dinitro-2,8,14,20-tetraoxa-
pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3(28),4,6,9(27),10,12,15(26),16,18,21,23-do-
decaene (8a). a. The reaction was carried out as de-
scribed above for the synthesis of 4a and 4b using
0.36 g (2 mmol) of tetrafluororesorcinol, 0.94 g
(2 mmol) of isomer mixture 1a/1b (86:14), and 1.0 g
(10 mmol) of triethylamine in 20 mL of acetonitrile
(reflux, 10 h). By silica gel column chromatography
we isolated 0.59 g (46%) of mixture 5a/5b at a ratio of
86:14 (GC/MS), and double recrystallization of that
mixture from carbon tetrachloride gave 0.29 g of 5a
with mp > 200°C.
19
3a and 3b at a ratio of 96:4 (GC/MS). F NMR spec-
trum (CCl4–CDCl3), δF, ppm: 3a: 2.0 t (1F, 5-F), 8.2 m
(4F, 2′-F, 2″-F, 6′-F, 6″-F), 10.6 d (2F, 4-F, 6-F), 12.8 s
(1F, 2-F), 16.4 m (4F, 3′-F, 3″-F, 5′-F, 5″-F); 3b: 1.8 t
(1F, 3′-F), 6.3 t (1F, 4″-F), 8.1 m (2F, 1-F, 5-F), 9.8 m
and 9.9 m (2F, 2′-F, 4′-F), 12.2 s (1F, 6′-F), 13.8 m (1F,
2″-F), 14.4 m (1F, 3″-F), 15.8 m (1F, 5″-F), 16.2 m (2F,
2-F, 4-F); in acetone-d6: 3a: 1.4 t (1F, 5-F), 8.7 m (4F,
2′-F, 2″-F, 6′-F, 6″-F), 11.2 d (2F, 4-F, 6-F), 14.6 s (1F,
2-F), 16.9 m (4F, 3′-F, 3″-F, 5′-F, 5″-F'); the 19F NMR
spectrum of 3a was consistent with that reported in
[23]. Mass spectrum: m/z: 568 [M]+.
4,5,17,18,26,28-Hexafluoro-6,16-dinitro-
2,8,14,20-tetraoxapentacyclo[19.3.1.13,7.19,13.115,19]-
octacosa-1(25),3(28),4,6,9(27),10,12,15(26),16,18,
21,23-dodecaene (4a) and 4,5,16,17,26,28-hexa-
fluoro-6,18-dinitro-2,8,14,20-tetraoxapenta-
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 11 5 , 1 9 ] o c t a c o s a -
1(25),3(28),4,6,9(27),10,12,15(26),16,18,21,23-do-
decaene (4b). A solution of 0.30 g (2,7 mmol) of
resorcinol and 1.48 g (~3 mmol) of isomer mixture
1a/1b (86:14) in 150 mL of acetonitrile was heated to
the boiling point, and a solution of 1.0 g (10 mmol) of
triethylamine in 5 mL of acetonitrile was added with
stirring. The mixture was refluxed for 16 h, the solvent
was distilled off under reduced pressure (~20 mm Hg),
and the residue was subjected to silica gel column
chromatography using carbon tetrachloride–chloroform
(~5:1 by volume) as eluent to isolate 1.04 g (62%) of
a product containing tetraoxacalixarenes 4a and 4b at
a ratio of 86:14. Double recrystallization of the product
from carbon tetrachloride gave 0.39 g of 4a with
mp > 200°C. IR spectrum (KBr), ν, cm–1: 1601, 1485 s
(C=Carom), 1552 s (NO2), 1365 m (NO2), 1244 s (C–O),
1166 s, 1115–1014 m (C–F). 19F NMR spectrum of 4a
(CCl4–CDCl3), δF, ppm: 11.4 d (2F, 4-F, 18-F, J =
23.0 Hz), 16.8 d.d (2F, 5-F, 17-F, J = 23.0, 10.0 Hz),
24.8 d (2F, 26-F, 28-F, J = 10.0 Hz). 1H NMR spectrum
of 4a (CCl4–CDCl3), δ, ppm: 5.84 s (1H, 25-H), 5.93 s
(1H, 27-H), 6.96 d.d (2H, 22-H, 24-H, J = 8.3, 2.3 Hz),
7.03 d.d (2H, 10-H, 12-H, J = 8.3, 2.3 Hz), 7.35 t (1H,
23-H, J = 8.3 Hz), 7.41 t (1H, 11-H, J = 8.3 Hz).
Found, %: C 50.59; H 1.69; F 20.09. m/z 568 [M]+.
C24H8F6N2O8. Calculated, %: C 50.90; H 1.42;
Compound 5a. IR spectrum (KBr), ν, cm–1: 1593,
1502 s (C=Carom), 1554 s (NO2), 1362 m (NO2), 1246 s
19
(C–O), 1167 s, 1146 s, 1107–1032 m (C–F). F NMR
spectrum, δF, ppm: in CDCl3: 2.6 t.d (1F, 11-F, J =
22.0, 5.0 Hz), 7.1 m (1F, 27-F), 8.7 d.d (2F, 10-F, 12-F,
J = 22.0, 2.0 Hz), 11.4 d (2F, 4-F, 18-F, J = 22.0 Hz),
17.2 d.d (2F, 5-F, 17-F, J = 22.0, 8.0 Hz), 18.1 d (2F,
26-F, 28-F, J = 8.0 Hz); in acetone-d6: 2.5 t.d (1F, 11-F,
J = 22.0, 5.0 Hz), 8.5 d.d (2F, 10-F, 12-F, J = 22.0,
2.0 Hz), 11.1 d (2F, 4-F, 18-F, J = 22.0 Hz), 11.5 m (1F,
27-F), 16.0 d.d (2F, 5-F, 17-F, J = 22.0, 8.0 Hz), 18.8 d
1
(2F, 26-F, 28-F, J = 8.0 Hz). H NMR spectrum, δ,
ppm: in CDCl3: 5.90 m (1H, 25-H), 7.07 d.d (2H,
22-H, 24-H, J = 8.3, 2.2 Hz), 7.44 t (1H, 23-H, J =
8.3 Hz); in acetone-d6): 6.86 m (1H, 25-H), 7.22 d.d
(2H, 22-H, 24-H, J = 8.3, 2.2 Hz), 7.59 t (1H, 23-H, J =
8.3 Hz). 13C NMR spectrum (acetone-d6), δC, ppm:
101.31 (C25), 114.81 (C22, C24), 130.43 d.d (C6, C16,
2JCF = 12.9, JCF = 3.5 Hz), 132.19 t (C3, C19 or C9, C13,
2JCF = 13.6 Hz), 133.03 (C23), 135.75 d (C7, C15, 2JCF
=
2
11.7 Hz), 137.22 t.d (C9, C13 or C3, C19, JCF = 12.8,
1
2
JCF = 3.7 Hz), 139.60 d.t.d (C11, JCF = 250.5, JCF
=
13.7, JCF = 4.3 Hz), 141.69 d.d (C10, C12, 1JCF = 252.9,
2JCF = 13.9 Hz), 142.54 d.d.d (C4, C18, JCF = 258.2,
1
1
2JCF = 14.9, JCF = 4.0 Hz), 142.91 d (C27, JCF
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

KOVTONYUK et al.
1158
1
2
251.8 Hz), 143.41 d.d.d (C5, C17, JCF = 253.6, JCF
=
=
1495 v.s (C=Carom), 1550 v.s (NO2), 1359 s (NO2),
1292 s (C–O), 1151 s, 1113–1007 s (C–F). 19F NMR
spectrum of 6a, δF, ppm: in CCl4–CDCl3: 11.1 d (2F,
4-F, 18-F, J = 23 Hz); 16.6 d.d (2F, 5-F, 17-F, J = 23.0,
10.0 Hz), 24.8 d (2F, 26-F, 28-F, J = 10.0 Hz); in
acetone-d6 (from the spectrum of mixture 6a/6b): 9.9 d
(2F, 4-F, 18-F, J = 23.0 Hz), 14.7 d.d (2F, 5-F, 17-F, J =
23.0, 10.0 Hz), 24.9 d (2F, 26-F, 28-F, J = 10 Hz).
1H NMR spectrum of 6a, δ, ppm: in CCl4–CDCl3:
2.34 s (3H, 23-CH3), 2.38 s (3H, 11-CH3), 5.64 s (1H,
25-H), 5.74 s (1H, 27-H), 6.80 d.d (2H, 22-H, 24-H,
J = 2.0, 1.0 Hz), 6.88 d.d (2H, 10-H, 12-H, J = 2.0,
1.0 Hz); in acetone-d6 (from the spectrum of mixture
6a/6b): 2.37 s (3H, 23-CH3), 2.41 s (3H, 11-CH3),
6.63 s (1H, 25-H), 6.73 s (1H, 27-H), 6.91 d (2H, 22-H,
24-H, J = 2.0 Hz), 7.00 d (2H, 10-H, 12-H, J = 2.0 Hz).
19F NMR spectrum of 6b (acetone-d6), δF, ppm (from
the spectrum of mixture 6a/6b): 10.0 d (2F, 4-F, 18-F,
J = 23.0 Hz), 14.7 m (2F, 5-F, 17-F), 25.0 d (2F,
13.8, JCF = 4.8 Hz), 144.27 d (C26, C28, JCF
1
252.9 Hz), 158.69 (C1, C21). Found, %: C 45.02;
H 0.85; F 30.10; N 4.39. m/z 634 [M]+. C24H4F10N2O8.
Calculated, %: C 45.16; H 0.63; F 29.76; N 4.39. 638.
Compound 5b. 19F NMR spectrum (CCl4–CDCl3),
δF, ppm (from the spectrum of mixture 5a/5b): 2.8 t.d
(1F, 11-F, J = 22.0, 5.0 Hz), 7.2 m (1F, 27-F), 8.4 d.d
and 9.2 d.d (2F, 10-F, 12-F, J = 22.0 Hz), 11.2 d and
11.7 d (2F, 4-F, 16-F, J = 23.0 Hz), 16.9 d.d and
17.0 d.d (2F, 5-F, 17-F, J = 23.0, 9.0 Hz), 17.5 d and
17.9 d (2F, 26-F, 28-F, J = 9.0 Hz).
b. Likewise, the reaction of 0.12 g (1.1 mmol) of
resorcinol with 0.65 g (1.1 mmol) of mixture 3a/3b
(96:4) in the presence of 0.7 g (7 mmol) of triethyl-
amine in 60 mL of acetonitrile under reflux for 13 h,
followed by appropriate treatment, gave 0.27 g (38%)
of a product containing 85% of 8a and 6% of 5b
(GC/MS). Recrystallization of the product from carbon
tetrachloride afforded 0.21 g of 8a. IR spectrum (KBr),
ν, cm–1: 1608 m, 1508 v.s, 1490 v.s (C=Carom), 1556 v.s
(NO2), 1365 m (NO2), 1246 m (C–O), 1173 m, 1162 m,
1
26-F, 28-F, J = 10.0 Hz). H NMR spectrum of 6b
(acetone-d6), δ, ppm (from the spectrum of mixture
6a/6b): 2.39 s (6H, 11-CH3, 23-CH3), 6.73 s (2H,
25-H, 27-H), 6.91 m (2H, 12-H, 24-H), 7.00 m (2H,
10-H, 22-H). Found for 6a, %: C 51.84; H 1.94;
F 19.93; N 4.60. m/z 594 [M]+. C26H12F6N2O8. Calcu-
lated, %: C 52.54; H 2.04; F 19.18; N 4.71. M 594.
19
1091–987 s (C–F). F NMR spectrum (CCl4–CDCl3),
δF, ppm: 3.2 t.d (1F, 11-F, J = 22.0, 5.0 Hz), 7.6 s (1F,
27-F), 9.0 d.d (2F, 10-F, 12-F, J = 22.0, 2.0 Hz), 10.6 d
(2F, 6-F, 16-F, J = 22.0 Hz), 17.1 d.d (2F, 5-F, 17-F, J =
22.0, 9.0 Hz), 17.5 d (2F, 26-F, 28-F, J = 9.0 Hz).
1H NMR spectrum (CCl4–CDCl3), δ, ppm: 5.86 s (1H,
25-H), 6.98 d.d (2H, 22-H, 24-H, J = 8.3, 2.3 Hz),
7.38 t (1H, 23-H, J = 8.3 Hz). Found: m/z: 637.9808
[M]+. C24H4O8N2F10. Calculated: M 637.9803.
4,5,10,11,12,17,18,26,27,28-Decafluoro-
23-methyl-6,16-dinitro-2,8,14,20-tetraoxapenta-
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 11 5 , 1 9 ] o c t a c o s a -
1(25),3(28),4,6,9(27),10,12,15(26),16,18,21,23-do-
decaene (7a) and 4,5,10,11,12,16,17,26,27,28-deca-
fluoro-23-methyl-6,18-dinitro-2,8,14,20-tetraoxa-
pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3(28),4,6,9(27),10,12,15(26),16,18,21,23-do-
decaene (7b) were synthesized as described above for
6a/6b from 0.29 g (2 mmol) of orcinol, 0.85 g
(4 mmol) of pentafluoronitrobenzene, and 0.46 g
(2.5 mmol) tetrafluororesorcinol using 2.0 g (20 mmol)
of triethylamine and 30 mL of acetonitrile; the mixture
was refluxed for 14 h. By silica gel column chromatog-
raphy we isolated 0.58 g (44%) of mixture 7a/7b
(80:20, GC/MS). Double recrystallization of that mix-
ture from carbon tetrachloride–light petroleum gave
0.30 g of 7a.
Compound 7a. IR spectrum (KBr), ν, cm–1: 1618 m,
1583 m, 1510 v.s, 1491 v.s (C=Carom), 1552 s (NO2),
1361 s (NO2), 1292 s (C–O), 1151 s, 1107 m, 1022 v.s
(C–F). 19F NMR spectrum (CDCl3), δF, ppm: 2.4 t.d
(1F, 11-F, J = 22.0, 5.0 Hz), 7.1 s (1F, 27-F), 8.7 d.d
(2F, 10-F, 12-F, J = 22.0, 2.0 Hz), 11.2 d (2F, 4-F, 18-F,
J = 23.0 Hz), 17.1 d.d (2F, 5-F, 17-F, J = 23.0, 8.0 Hz),
18.1 d (2F, 26-F, 28-F, J = 8.0 Hz). 1H NMR spectrum
4,5,17,18,26,28-Hexafluoro-11,23-dimethyl-
6 , 1 6 - d i n i t r o - 2 , 8 , 1 4 , 2 0 - t e t r a o x a p e n t a -
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 11 5 , 1 9 ] o c t a c o s a -
1(25),3(28),4,6,9(27),10,12,15(26),16,18,21,23-
dodecaene (6a) and 4,5,16,17,26,28-hexafluoro-
11,23-dimethyl-6,18-dinitro-2,8,14,20-tetraoxa-
pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3(28),4,6,9(27),10,12,15(26),16,18,21,23-do-
decaene (6b). A solution of 2.0 g (20 mmol) of tri-
ethylamine in 10 mL of acetonitrile was added with
stirring to a solution of 0.29 g (2 mmol) of orcinol and
0.85 g (4 mmol) of pentafluoronitrobenzene in 30 mL
of acetonitrile, cooled to 0°C. The mixture was stirred
for 1 h at 0°C and for 1 h at room temperature, 110 mL
of acetonitrile and 0.29 g (2 mmol) of orcinol were
added, and the mixture was refluxed for 33 h. The
solvent was distilled off, and the residue was subjected
to chromatography to isolate 0.73 g (61%) of a mixture
of 6a and 6b (84:16, GC/MS). Double recrystallization
of the product from carbon tetrachloride gave 0.44 g
of 6a. IR spectrum (KBr), ν, cm–1: 1618 s, 1591 s,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

SYNTHESIS OF POLYFLUORINATED TETRAOXACALIX[4]ARENES
1159
9. Wang, D.-X. and Wang, M.-X., J. Am. Chem. Soc., 2013,
vol. 135, p. 892.
(CDCl3), δ, ppm: 2.38 s (3H, 23-CH3), 5.69 s (1H,
25-H), 6.88 m (2H, 22-H, 24-H). Found: m/z 651.9955
[M]+. C25H6O8N2F10. Calculated: M 651.9959.
Compound 7b. 19F NMR spectrum (CCl4–CDCl3),
δF, ppm (from the spectrum of mixture 7a/7b): 2.6 t.d
(1F, 11-F, J = 22.0, 5.0 Hz), 7.6 s (1F, 27-F), 8.5 d.d
(1F, J = 22.0, 2.0 Hz), 9.2 d.d (1F, J = 22.0, 2.0 Hz)
(10-F, 12-F), 11.0 d and 11.6 d (1F each, 4-F, 18-F, J =
23.0 Hz), 16.8 d.d (2F, 5-F, 17-F, J = 23.0, 9.0 Hz),
17.8 d and 18.1 d (1F each, 26-F, 28-F, J = 9.0 Hz).
https://doi.org/10.1021/ja310834w
10. Li, S., Fa, S.-X., Wang, Q.-Q., Wang, D.-X., and
Wang, M.-X., J. Org. Chem., 2012, vol. 77, p. 1860.
https://doi.org/10.1021/jo2024448
11. Liu, W., Wang, Q.-Q., Wang, Y., Huang, Z.-T., and
Wang, D.-X., RSC Adv., 2014, vol. 4, p. 9339.
https://doi.org/10.1039/c3ra47748g
12. He, Q., Ao, Y.-F., Huang, Z.-T., and Wang, D.-X., Angew.
Chem., Int. Ed., 2015, vol. 54, p. 11785.
https://doi.org/10.1002/anie.201504710
13. He, Q., Han, Y., Wang, Y., Huang, Z., and Wang, D.,
Chem. Eur. J., 2014, vol. 20, p. 7486.
ACKNOWLEDGMENTS
https://doi.org/10.1002/chem.201400074
14. He, Q., Huang, Z.-T., and Wang, D.-X., Chem. Commun.,
2014, vol. 50, p. 12985.
The authors thank the Joint Chemical Service Center,
Siberian Branch, Russian Academy of Sciences, for
providing facilities for analytical and spectral studies.
https://doi.org/10.1039/C4CC05924G
15. Wang, X.-D., Li, S., Ao, Y.-F., Wang, Q.-Q.,
Huang, Z.-T., and Wang, D.-X., Org. Biomol. Chem.,
2016, vol. 14, p. 330.
FUNDING
H. Han thanks the State Fellowship Committee of the
People Republic of China for financial support.
https://doi.org/10.1039/c5ob02291f
16. Mehta, V., Athar, M., Jha, P.C., Panchal, M., Modi, K.,
and Jain, V.K., Bioorg. Med. Chem. Lett., 2016, vol. 26,
p. 1005.
CONFLICT OF INTEREST
The authors declare no conflict of interest.
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