Fluorinated allyl-, acetyl-, and bromo-containing hydroxyl-substituted phenyl ethers with a hexafluorobenzene or decafluorobiphenyl central unit

Article abstract of DOI:10.1016/j.jfluchem.2013.02.009

We report on methods of synthesis of new hexafluorobenzene- and decafluorobiphenyl-based hydroxyl-substituted phenyl ethers containing allyl, acetyl groups, and bromine atoms. Optimal conditions for Claisen and Fries rearrangements used during the synthesis of these fluorinated compounds are discussed. The resulting compounds can be employed as monomers for synthesis of a wide variety of nucleus-fluorinated aromatic polymers suitable for optical or membrane applications.

Full text of DOI:10.1016/j.jfluchem.2013.02.009

Accepted Manuscript
Title: Fluorinated allyl-, acetyl-, and bromo-containing
hydroxyl-substituted phenyl ethers with a hexafluorobenzene
or decafluorobiphenyl central unit
Authors: Igor Tkachenko, Oleg Shekera, Valery Bliznyuk,
Valery Shevchenko
PII:
S0022-1139(13)00067-5
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.jfluchem.2013.02.009
FLUOR 8048
To appear in:
FLUOR
Received date:
Revised date:
Accepted date:
15-11-2012
5-2-2013
6-2-2013
Please cite this article as: I. Tkachenko, O. Shekera, V. Bliznyuk, V. Shevchenko,
Fluorinated allyl-, acetyl-, and bromo-containing hydroxyl-substituted phenyl ethers
with a hexafluorobenzene or decafluorobiphenyl central unit, Journal of Fluorine
Chemistry (2013), http://dx.doi.org/10.1016/j.jfluchem.2013.02.009
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Fluorinated allyl-, acetyl-, and bromo-containing hydroxyl-
substituted phenyl ethers with a hexafluorobenzene or
decafluorobiphenyl central unit
Igor Tkachenkoa, Oleg Shekeraa, Valery Bliznyukb, Valery Shevchenkoa*
aInstitute of Macromolecular Chemistry of the National Academy of
Sciences of Ukraine, 48, Kharkivske shosse, Kiev, 02160, Ukraine
bMaterials Science and Engineering Department, Clemson University,
Clemson, South Carolina, 29634 USA
__________________________
*Corresponding author. Tel.; +38-044-559-5500; FAX: +38-044-292-4064.
E-mail address: valshevchenko@yandex.ru (Valery Shevchenko).
Page 1 of 33

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ABSTRACT
We report on methods of synthesis of new hexafluorobenzene- and
decafluorobiphenyl-based hydroxyl-substituted phenyl ethers containing
allyl, acetyl groups, and bromine atoms. Optimal conditions for Claisen and
Fries rearrangements used during the synthesis of these fluorinated
compounds are discussed. The resulting compounds can be employed as
monomers for synthesis of a wide variety of nucleus-fluorinated aromatic
polymers suitable for optical or membrane applications.
Keywords: hexafluorobenzene-containing monomers, decafluorobiphenyl-
containing monomers, Claisen rearrangement, Fries rearrangement,
bromination, hydrogen bond.
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1. Introduction
Fluorinated aromatic polycondensation polymers represent a
prospective recent trend in development of thermally stable organic
compounds [1-3]. Introduction of perfluorinated aromatic fragments to a
polymer backbone allows reduction of the polymer’s dielectric constant,
the refractive index, optical and dielectric losses making such materials
attractive for modern hi-tech applications in microelectronics, aerospace
industry, and, especially, in optical telecommunications [1, 3-8].
Synthesis of such compounds is typically accomplished with an
application of monomers containing hexafluorobenzene (HFB) or
decafluorobiphenyl (DFB) fragments [1, 3-10]. Usage of the HFB and DFB
units as individual monomers presents a certain limitation, since only
nucleus-fluorinated aromatic polyethers can be synthesized within such
chemical route [1, 11].
A broader application of perfluorinated aromatic polymers depends on
diversification of their chemical functionalization through polymer
analogous transformations, or by means of monomer units containing
functional groups or fragments [1, 6, 7, 12-15]. The latter strategy typically
employs a combination of two monomer units: one being fluorinated and
another one with appropriate functional groups [14-17]. An alternative
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4
approach, in which the same monomer is fluorinated and simultaneously
contains functional groups is less developed.
Thus, synthesis of new monomers based on HFB and DFB units and
containing functional groups is crucial for further development in the field.
In this context, the most promising are hydroxyl-containing building
blocks, which include perfluorinated mono- or biphenylene units separated
from OH groups with oxyphenylene fragments. The presence of the
hydroxyl groups allows synthesis of a broad range of polymers (such as
polyesters, polyethers, polyarylates, polyurethanes etc.).
Previously we reported on the first successful synthesis of nucleus-
fluorinated aromatic polyethers having both HFB and DFB units in the
backbone [18]. Hydroxyl-containing derivatives of HFB units were used as
monomers for their synthesis. Functionalization of such compounds with
aminomethyl fragments allowed their usage as monomers for the synthesis
of film-forming aromatic polyethers prospective for ion-exchange
membrane applications [19, 20].
In this paper, we report on methods of synthesis of novel fluorinated
allyl-, acetyl-, and bromo-containing hydroxyl-substituted phenyl ethers
with HFB and DFB fragments. When being used as monomers, they will
enable synthesis of a broad range of different classes of functional
perfluorinated polymers.
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2. Results and discussion
The developed method of synthesis of new monomers 5 and 6
containing allyl groups is based on converting compounds 1 and 2 into
their diallyl ethers (3 and 4 respectively) followed by the Claisen
rearrangement reaction performed in an absence of the solvent (Scheme 1).
Conditions of the synthesis of monomers 5 and 6 were studied on the
example of the compound 5. It was found that the optimum conditions of
the Claisen rearrangement are the temperature 210оC and the duration of 30
min. A mixture of monomers could be obtained by decreasing the reaction
time to 10 min. However, this mixture was too difficult to separate into
components. The increase of the rearrangement temperature to 240оC (30
min) reduced the yield of the monomer 5 to 45%. It is noteworthy that the
yield of diallyl ether 3 significantly increased with increasing the reaction
time from 12 to 20 hours.
The structure of the synthesized compounds was determined by IR, 1H
NМR, 19F NMR, 13C NMR and mass spectrometry techniques. The
formation of the diallyl ether 3 and 4 is confirmed by disappearance of a
broad band in their IR spectra in the region of 3200-3600 cm-1, which is the
characteristic signature for OH groups of the initial compounds 1 and 2
(Fig. 1). Also, one can observe new absorption bands at 927 cm-1 for the
compound 3 and 924 cm-1 for compound 4, which indicates on the presence
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6
of vinyl groups of the allyl fragments. The absorption bands of vinyl
groups are preserved in the IR spectra of the allyl-containing monomers 5
and 6. The presence of the OH groups in these monomers is confirmed by
the appearance of the corresponding absorption bands. However, Fig. 1
shows that while in the compound 5 the characteristic absorption band of
the OH groups is broad and has a maximum at 3323 cm-1, the same band is
narrower and shifted to higher frequencies (3506cm-1) for the compound 6.
These data indicate formation of intermolecular hydrogen bonds in a
crystalline form of the monomer 5, whereas the hydroxyl groups of the
monomer 6 (crystalline form) remain predominantly non-associated.
Obviously, this difference is due to steric hindrances associated with the
presence of non-planar tetrafluorobenzene’s nucleus characteristic for the
octafluorobiphenyl fragment of monomer 6 [21]. In addition, one can
assume an important role of the allyl fragments, as the hydrogen bonds
were proved to exist in the crystalline form of compound 2 [22].
The effect of the solvent polarity could be also recognized by
comparing the ability of the compound 5 to form hydrogen bonds in its
mixtures with less polar (chloroform) or more polar (Me2SO) solvents (Fig.
2). It was found that the chemical shift corresponding to the protons of
hydroxyl groups (g) of the compound 5 in chloroform was shifted to
stronger field direction and was equal to 4.87 ppm. A similar trend was
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7
observed for the compound 6 in the same solvent (Fig. 2). These data
indicate the basic nature of the hydroxyl groups of monomers 5 and 6 in
chloroform solutions and consequently presence of less-developed network
of hydrogen bonds in the system. At the same time, monomer 5 forms
strong hydrogen bonds in the solution of the polar solvent (Me2SO), as
indicated by the displacement of the chemical shift being characteristic for
OH groups in a weak field (9.32 ppm). Interestingly, similar results were
obtained for compounds 1 and 2 in previous studies [22].
1
Other chemical shifts revealed in the H NМR spectra of monomers 5
and 6 correspond well to the proposed structures.
Acetyl-containing monomers 9 and 10 were synthesized in two steps
similarly to allyl-containing ones. During the first stage, acetylation of the
compounds 1 or 2 led to formation of esters 7 or 8 (Scheme 1). During the
second stage of chemical transformations, monomers 9 and 10 were
obtained by Fries rearrangement reactions in a presence of AlCl3. It was
also shown that the rearrangement reactions do not occur at room
temperature or at the boiling point in case of a dichloromethane solution.
Neither there was possible to separate pure monomer 9 in a route the
rearrangement reaction in nitrobenzene. On the other hand, carrying out the
second step (rearrangements of Fries reaction) in the absence of any solvent
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8
at elevated temperatures of 175 - 180°C was found to be the most suitable
condition to increase the yield of the acetyl-containing monomers.
The effect of the AlCl3 amount on the route and duration of the Fries
rearrangement reaction during synthesis of the compound 7 was studied by
1H NМR spectroscopy. We have found that the optimum molar ratio of
AlCl3 to compound 7 was 4 to 1. If the ratio was decreased (3 moles of
AlCl3 to 1 mole of compound 7) the yield of monomer 9 was reduced to
almost one half. In addition, if this ratio was lower (2 moles of AlCl3 to 1
mole of compound 7) a mixture of various monomers with not fully
detectable structure was obtained. The reaction was carried out without
solvents, which required quite a large excess of AlCl3. Moreover, partial
deactivation of AlCl3 molecules is possible due to their reaction with OH
groups arising as a result of the Fries rearrangement as described in Ref.
[23]. We have found also that the Fries rearrangement reaction requires at
least 10 hours for its completion. When the reaction time was shorter (6 or
8 hours) a considerable amount of the original and obviously mono-
rearranged compound 7 remained in the final product as could be evident
from the 1H NМR spectra presented in Fig. 3. The corresponding chemical
shifts of the original and mono-rearranged compound 7 are marked with an
asterisk in the figure.
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Note that the absorption bands corresponding to the hydroxyl groups
in the IR spectra of monomers 9 and 10 are very broad and have low
intensity (Fig. 1). These results indicate that the latter compounds possess a
well-developed network of hydrogen intra- and intermolecular bonds (in
particular due to the presence of acetyl groups in the ortho-position to the
OH groups).
1H NМR spectra of the synthesized monomers 9 and 10 correspond to
the proposed structures (Fig. 3); they all contain a singlet peak in a weak
field (12.04 - 12.07 ppm) corresponding to the two protons of hydroxyl
groups (e). Moreover, unlike to the case of allyl-containing monomers 5
and 6, chemical shifts of protons of the OH groups in monomers 9 and 10
are not considerably affected by the choice of a solvent.
Fluorine-containing brominated monomers 11 and 12 were obtained
by the reaction of bromine with the initial compounds 1 and 2 respectively
(Scheme 2).
When the compound 1 was brominated, a partially brominated
intermediate product precipitated from the solution, which caused further
bromination reactions to occur in a suspension. On contrary, bromination
of the compound 2 proceeded completely in the solution.
Similarly to the allyl-containing monomer 6, the absorption bands
corresponding to vibrations of OH groups in IR spectra of compounds 11
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10
and especially compound 12 are quite narrow (Fig. 1). The absence of a
developed network of hydrogen bonds in this case is associated with steric
constraints that arise from the presence of bromine atoms in the monomers
11 and 12. 1H NМR spectra of monomers 11 and 12 show two singlets; one
corresponding to four equivalent protons of the aromatic nuclei and another
corresponding to protons in the hydroxyl groups. Brominated monomers
are able to form strong hydrogen bonds when dissolved in a polar solvent.
1
This is manifested by the presence of singlet peaks in the H NМR
spectrum of the monomer 11 corresponding to the protons of OH groups in
a weak field similarly to the singlet peak observed in the monomer 12. The
spectrum of the latter is taken in chloroform. As mentioned above, similar
characteristic spectra have been observed for monomers 5 and 6.
13
The C NMR spectra of the synthesized compounds 3-12 (Fig. 4)
correspond to the proposed structures. Development of the rearrangements
of Claisen or Fries can be tracked by the appearance of two additional
13
chemical peaks in the C NMR spectra of monomers 5, 6, 9 and 10 in
comparison to the corresponding spectra of the initial ethers 3, 4, 7 and 8.
These additional peaks correspond to carbon atoms of nonfluorinated
aromatic nuclei. Moreover, the chemical peak at 69 ppm, which
corresponds to carbon atoms of the methylene group of the allyl fragment
of compound 3 and 4 is displaced towards stronger shift region (35 ppm) in
Page 10 of 33

11
appropriate monomers 5 and 6. On the other hand, NMR peak with the
chemical shift of 169 ppm corresponding to carbon atoms of the carbonyl
group in compounds 7 and 8 is displaced towards weaker chemical shift
13
region (203 ppm) in appropriate monomers 9 and 10. Fig. 4 presents C
NМR spectra of synthesized compounds 7 and 9 as an example.
As expected, all the compounds containing the tetrafluorobenzene
fragments (3, 5, 7, 9, 11) received in this work show a singlet peak in their
19F NMR spectra from the four equivalent fluorine atoms. Similar spectra
of the compounds containing octafluorobiphenylene nucleus (4, 6, 8, 10,
12) are characterized by the presence of two singlets, which belong to
fluorine atoms of the perfluorinated biphenylene fragment in the meta- and
ortho-positions.
Allyl-, acetyl-, and bromine-containing compounds are white powders
(monomers 9 and 10 are pale yellow) and mostly soluble in
dimethylformamide, dimethylacetamide, tetrahydrofuran, N-methyl
pyrrolidone, acetone, chloroform and some other dipolar solvents.
The suggested monomers unit design enables further chemical
modifications through so-called thiol-ene chemistry [24-26], or
hydrosilylation reactions [27-29] (using allyl fragments). Also, specific
reactions by Mannich, Claisen-Schmidt condensation (using acetyl groups)
[30, 31], Suzuki (using bromine atoms) [32], or some other mechanisms
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12
become possible in this case. Moreover, application of the above
mentioned functional groups in a polycondensation reaction offers
polymers compounds with an alternation of highly hydrophobic
perfluorinated aromatic units and OH groups along the polymer chain [33,
34]. These macromolecules can simultaneously combine fluorine and
bromine atoms in their structure and, therefore, may possess interesting
optical properties [35]. Additionally, due to existence of perfluorinated
aromatic units in their structure these monomers are capable for
nucleophilic substitution reactions [36], that further extends the range of
their possible applications.
3. Conclusions
We have studied and developed synthetic routes for several new
nucleus-fluorinated aromatic monomers containing allyl or acetyl
fragments and bromine atoms. Optimal conditions for Claisen and Fries
rearrangements were found and described. The presence of two hydroxyl
groups opens the possibility of using such compounds in macromolecular
chemistry for the synthesis of a wide range of nucleus-fluorinated
polymers. Moreover, the presence of functional groups enables new
properties and offers interesting opportunities for further functionalization
of such polymers (creation of multifunctional polymer systems).
4. Experimental
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4. 1. Materials
4-[2,3,5,6-tetrafluoro-4-(4-hydroxyphenoxy)phenoxy]phenol (1) and 4-
{2,3,5,6-tetrafluoro-4-[2,3,5,6-tetrafluoro-4-(4-
hydroxyphenoxy)phenyl]phenoxy}phenol (2) were synthesized according
to the previously reported procedure [22]. Allyl bromide (99%, Acros
Organics), AlCl3, and bromine (Merk) were used without further
purification. Other reagents and solvents were purified by well established
techniques.
4. 2. Measurements
FTIR spectra (4000-600 сm-1) were recorded on a “TENSOR 37” Fourier
1
13
19
transform infrared spectrometer using KBr pellets. H, C, and F NMR
spectra of compounds were measured on a Bruker model DRX 500 Avance
13
apparatus in CDCl3 or Me2SO-d6 with tetramethylsilane (1H NMR and C
NMR) or HFB (19F) as an internal standard at the following frequencies: 1H
13
19
500 МHz, C 125.75 MHz, and F 188.14 MHz. The mass spectra were
acquired with a PE SCIEX API 150 EX mass spectrometer equipped with
UV (254 nm) and ELSD detectors.
4. 3. Monomer synthesis
4. 3. 1. 1,2,4,5-tetrafluoro-3,6-bis[4-(prop-2-en-1-yloxy)phenoxy]benzene
(3)
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A 100-mL round-bottom flask was charged with compound 1 (3.00 g, 8.19
mmol), allyl bromide (2.18 g, 18.02 mmol), potassium carbonate (2.83 g,
20.48 mmol) and acetone (37 mL). The mixture was stirred and heated
under reflux for 20 h. Then, the mixture was cooled to room temperature
and poured dropwise into ice-water to precipitate the product. The
precipitate was filtered and washed with NaOH (10 wt.%) solution and
water several times. The resulting product was recrystallized from
1
isopropyl alcohol. Yield: 80%; m.p.: 107-108oC. H NMR (CDCl3, δ,
ppm): 4.52 (d, 4H, J=5.4 Hz, -СН2-), 5.32 (ddd, 2H, Jcis=10.8; 1.5; 0.98 Hz,
а
b
=СН2 ), 5.44 (ddd, 2H, Jtrans=17.6; 1.5; 0.98 Hz, =СН2 ), 6.03-6.10 (m, 2Н,
13
=СН-), 6.90 (d, 4Н, J=9.3 Hz, Ph), 6.96 (d, 4Н, J=9.3 Hz, Ph). C NMR
(CDCl3, δ, ppm): 69.37 (-CH2), 115.74, 116.84 (Ar-C), 117.71 (=CH2),
131.20 (ArF-C(O)) 133.13 (CH=), 141.23, 143.25 (C-F), 151.53 (Ar-C(O)),
155.03 (C-O-Allyl). 19F NMR (CDCl3, δ, ppm): -156.03 (s, 4F, Ph). FT-IR
(ν, сm-1): 927 (СН2=СН), 988 (C-F), 1240 (Ar-O-Ar), 1504 (С=Сarom),
2800-3100 (СН). ELSD-MS: m/z = 447 [M+ 1]+.
4. 3. 2. 1,2,4,5-tetrafluoro-3-[4-(prop-2-en-1-yloxy)phenoxy]-6-{2,3,5,6-
tetrafluoro-4-[4-(prop-2-en-1-yloxy)phenoxy]phenyl}benzene (4)
The compound 4 was prepared in the same manner as 3, with compound 2
used instead of compound 1. Yield: 75%; m.p.: 93-94oC. 1H NMR (CDCl3,
δ, ppm): 4,55 (d, 4H, J=4.89 Hz, -СН2-), 5.33 (ddd, 2H, Jcis=10.3; 0.97;
Page 14 of 33

15
а
b
0.97 Hz, =СН2 ), 5.44 (ddd, 2H, Jtrans=17.6; 1.5; 0.98 Hz, =СН2 ), 6.03-
6.11 (m, 2Н, =СН-), 6.93 (d, 4Н, J=8.8 Hz, Ph), 7.02 (d, 4Н, J=9.3 Hz,
13
Ph). C NMR (CDCl3, δ, ppm): 69.42 (-CH2), 102.25 (ArF-C-C-ArF),
115.74, 117.21 (Ar-C), 117.78 (=CH2), 133.05 (CH=), 136.31 (ArF-C(O)),
140.72, 142.82, 143.92, 145.78 (C-F), 151.14 (Ar-C(O)), 155.29 (C-O-
19
Allyl). F NMR (CDCl3, δ, ppm): -139.52 (s, 4F, Ph), -154.7 (s, 4F, Ph).
FT-IR (ν, сm-1): 924 (СН2=СН), 980 (C-F), 1244 (Ar-O-Ar), 1497
(С=Сarom.), 2800-3100 (СН). ELSD-MS: m/z = 595 [M+ 1]+.
4. 3. 3. 2-(prop-2-en-1-yl)-4-{2,3,5,6-tetrafluoro-4-[4-hydroxy-3-(prop-2-
en-1-yl)phenoxy]phenoxy}phenol (5)
The monomer 3 (2 g, 4.48 mmol) was kept at 210оС under argon gas for 30
min to carry out Claisen rearrangement reaction. Thus obtaining monomer
5, was crystallized by cooling the reagent to room temperature and then
purified by crystallization from heptanes solution. Yield: 75%; m.p.: 124-
127oC. 1Н NMR (Me2SO-d6, δ, ppm): 3.29 (d, 4H, J=6.2 Hz, -СН2-), 5.00-
5.06 (m, 4H, =СН2), 5.90-6.00 (m, 2Н, =СН-), 6.75-6.88 (m, 6Н, Ph), 9.32
(s, 2H, OH). 13C NMR (CDCl3, δ, ppm): 35.08 (-CH2), 114.85, 116.54 (Ar-
C), 116.99 (=CH2), 118.02 (Ar-C), 127.01 (Ar-C(CH2)), 135.62 (CH=),
131.16 (ArF-C(O)), 141.21, 143.35 (C-F), 150.39 (Ar-C(O)), 151.41 (C-
19
OH). F NMR (CDCl3, δ, ppm): -156.04 (s, 4F, Ph). FT-IR (ν, сm-1): 914
Page 15 of 33

16
(СН2=СН), 993 (C-F), 1250 (Ar-O-Ar), 1499 (С=Сarom), 2800-3000 (СН),
3100-3600 (ОН). ELSD-MS: m/z = 447 [M+ 1]+.
4. 3. 4. 2-(prop-2-en-1-yl)-4-(2,3,5,6-tetrafluoro-4-{2,3,5,6-tetrafluoro-4-
[4-hydroxy-3-(prop-2-en-1-yl)phenoxy]phenyl}phenoxy)phenol (6)
The monomer 6 was prepared in the same manner as compound 5, with
compound 4 used instead of the monomer 3. Yield: 70%; m.p.: 108-111oC.
1Н NMR (CDCl3, δ, ppm): 3.42 (d, 4H, J=5.9 Hz, -СН2-), 4.87 (s, 2H, OH),
5.19-5.23 (m, 4H, =СН2), 5.99-6.07 (m, 2Н, =СН-), 6.91 (d, 2Н, J=7.8 Hz,
13
Ph), 6.84 (d, 2Н, J=7.8 Hz, Ph), 6.83 (s, 2Н, Ph). C NMR (CDCl3, δ,
ppm): 35.06 (-CH2), 102.18 (ArF-C-C-ArF), 115.17, 116.52 (Ar-C), 117.05
(=CH2), 118.37 (Ar-C), 127.10 (Ar-C(CH2)), 135.48 (CH=), 136.32 (ArF-
C(O)), 140.69, 142.80, 143.82, 145.78 (C-F), 150.70 (Ar-C(O)), 151.03 (C-
19
OH). F NMR (CDCl3, δ, ppm): -139.46 (s, 4F, Ph), -154.66 (s, 4F, Ph).
FT-IR (ν, сm-1): 926 (СН2=СН), 974 (C-F), 1242 (Ar-O-Ar), 1489
(С=Сarom.), 2850-3000 (СН), 3500 (ОН). ELSD-MS: m/z = 595 [M+ 1]+.
4. 3. 5. 4-{4-[4-(acetyloxy)phenoxy]-2,3,5,6-tetrafluorophenoxy}phenyl
acetate (7)
A catalytic amount of sulfuric acid was added to a solution of the
compound 1 (2 g, 5.46 mmol) in acetic anhydride (10 mL). The reaction
mixture was refluxed for 30 min. After cooling to room temperature the
solution was diluted with water. The resulting precipitate was collected by
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17
filtration and washed with D.I. water. Isolation product was purified by
1
crystallization from ethanol. Yield: 98%; m.p.: 172-174oC. H NMR
(CDCl3, δ, ppm): 2.32 (s, 6H, -СН3), 7.03 (d, 4Н, J=8.8 Hz, Ph), 7.09 (d,
4Н, J=9.3 Hz, Ph). 13C NMR (CDCl3, δ, ppm): 20.87 (CH3), 116.35, 122.69
(Ar-C), 130.87 (ArF-C(O)), 141.21, 143.23 (C-F), 146.66 (Ar-C(O)),
154.66 (C-OAc), 169.36 (C=O). 19F NMR (CDCl3, δ, ppm): -155.16 (s, 4F,
Ph). FT-IR (ν, сm-1): 993 (C-F), 1219 (Ar-O-Ar), 1493 (С=Сarom.), 1765
(С=О). ELSD-MS: m/z = 451 [M+ 1]+.
4. 3. 6. 4-(4-{4-[4-(acetyloxy)phenoxy]-2,3,5,6-tetrafluorophenyl}-2,3,5,6-
tetrafluorophenoxy)phenyl acetate (8)
The compound 8 was prepared in the same manner as diacetate 7, with
compound 2 used instead of compound 1. Yield: 90%; m.p.: 158-160oC. 1H
NMR (CDCl3, δ, ppm): 2.32 (s, 6H, -СН3), 7.09 (d, 4Н, J=8.8 Hz, Ph), 7.12
13
(d, 4Н, J=9.3 Hz, Ph). C NMR (CDCl3, δ, ppm): 20.93 (CH3), 102.65
(ArF-C-C-ArF), 116.71, 122.77 (Ar-C), 135.45 (ArF-C(O)), 140.68, 142.71,
143.76, 145.75 (C-F), 146.89 (Ar-C(O)), 154.35 (C-OAc), 169.31 (C=O).
19F NMR (CDCl3, δ, ppm): -139.02 (s, 4F, Ph), -154.0 (s, 4F, Ph). FT-IR (ν,
сm-1): 980 (C-F), 1221 (Ar-O-Ar), 1493 (С=Сarom.), 1758 (С=О). ELSD-
MS: m/z = 599 [M+ 1]+.
4. 3. 7. 1-{5-[4-(3-acetyl-4-hydroxyphenoxy)-2,3,5,6-tetrafluorophenoxy]-
2-hydroxyphenyl}ethan-1-one (9)
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18
A mixture of diacetate 7 (2 g, 4.44 mmol) and anhydrous aluminum
chloride (2.37 g, 17.8 mmol) was finely powdered in a mortar and
introduced into a 50-mL round-bottom flask. The reaction mixture was
heated slowly to 175оС in an oil bath and maintained at that point for 10 h
under argon. A crushed ice and concentrated HCl were added to the
reaction mixture after its cooling. The resulting mixture was stirred for 15
min and the crude product was filtered, washed with D.I. water and
1
crystallized twice from decane. Yield: 70%; m.p.: 189-191oC. H NMR
(CDCl3, δ, ppm): 2.64 (s, 6H, -СН3), 7.0 (d, 2Н, J=8.8 Hz, Ph), 7.17 (d, 2Н,
13
J=8.8 Hz, Ph), 7.47 (s, 2H, Ph), 12.04 (s, 2H, OH). C NMR (CDCl3, δ,
ppm): 26.3 (CH3), 117.61 (Ar-C), 119.43 (Ar-C(C=O)), 119.80, 124.74
(Ar-C), 131.29 (ArF-C(O)), 141.19, 143.14 (C-F), 149.03 (Ar-C(O)),
19
158.94 (C-OH), 203.59 (C=O). F NMR (CDCl3, δ, ppm): -155.41 (s, 4F,
Ph). FT-IR (ν, сm-1): 988, 1015 (C-F), 1238 (Ar-O-Ar), 1510 (С=Сarom.),
1655 (С=О), 3000-3600 (ОН). ELSD-MS: m/z = 451 [M+ 1]+.
4. 3. 8. 1-(5-{4-[4-(3-acetyl-4-hydroxyphenoxy)-2,3,5,6-tetrafluorophenyl]-
2,3,5,6-tetrafluorophenoxy}-2-hydroxyphenyl)ethan-1-one (10)
The monomer 10 was prepared in the same manner as 9, with compound 8
1
instead of diacetate 7. Yield: 65%; m.p.: 183-185oC. H NMR (CDCl3, δ,
ppm): 2.66 (s, 6H, -СН3), 7.03 (d, 2Н, J=8.8 Hz, Ph), 7.24 (dd. 1Н, J=9.3;
2.9 Hz, Ph), 7.26 (dd 1Н, J=9.3; 2.9 Hz, Ph), 7.52 (d, 2H, J=2.9 Hz, Ph),
Page 18 of 33

19
13
12.07 (s, 2H, OH). C NMR (CDCl3, δ, ppm): 26.52 (CH3), 101.73 (ArF-
C-C-ArF), 117.96 (Ar-C), 119.45 (Ar-C(C=O)), 119.76, 125.10 (Ar-C),
136.13 (ArF-C(O)), 140.52, 142.64, 143.88, 145.92 (C-F), 148.67 (Ar-
C(O)), 159.16 (C-OH), 203.62 (C=O). 19F NMR (CDCl3, δ, ppm): -138.81
(s, 4F, Ph), -154.5 (s, 4F, Ph). FT-IR (ν, сm-1): 978 (C-F), 1248 (Ar-O-Ar),
1489 (С=Саarom.), 1655 (С=О), 3000-3600 (ОН). ELSD-MS: m/z = 599
[M+ 1]+.
4. 3. 9. 2,6-dibromo-4-[4-(3,5-dibromo-4-hydroxyphenoxy)-2,3,5,6-
tetrafluorophenoxy]phenol (11)
Solution of bromine (0.56 mL, 10.92 mmol) in 5 mL acetic acid was added
dropwise to a solution of the compound 1 (1 g, 2.73 mmol) in 9 mL of
glacial acetic acid under stirring at 90oC. The reaction mixture was stirred
vigorously at 90oC for 4 h until the white product precipitated out from the
solution. Then, the mixture was cooled to room temperature and poured
into ice-water. The precipitate was filtered and washed with D.I. water.
Resulting product was purified by crystallization from acetic acid. Yield:
1
85%; m.p.: 235-237oC. H NMR (Me2SO-d6, δ, ppm): 7.54 (s, 4H, Ph),
13
9.85 (s, 2H, OH). C NMR (Me2SO-d6, δ, ppm): 112.31 (C-Br), 119.04
(Ar-C), 129.73 (ArF-C(O)), 140.75, 142.67 (C-F), 147.50 (Ar-C(O)), 149.9
19
(C-OH). F NMR (Me2SO-d6, δ, ppm): -155.64 (s, 4F, Ph). FT-IR (ν, см-
Page 19 of 33

20
1): 791, 899 (C-Br), 991 (C-F), 1229 (Ar-O-Ar), 1468 (С=Сarom.), 3441
(ОН). ELSD-MS: m/z = 683 [M+ 1]+.
4. 3. 10. 2,6-dibromo-4-{4-[4-(3,5-dibromo-4-hydroxyphenoxy)-2,3,5,6-
tetrafluorophenyl]-2,3,5,6-tetrafluorophenoxy}phenol (12)
The monomer 12 was prepared in the same manner as monomer 11, with
compound 2 used instead of compound 1. Yield: 70%; m.p.: 158-160oC. 1H
13
NМR (CDCl3, δ, ppm): 5.83 (s, 2H, OH), 7.26 (s, 4H, Ph). C NMR
(CDCl3, δ, ppm): 103.09 (ArF-C-C-ArF), 109.93 (C-Br), 120.40 (Ar-C),
135.52 (ArF-C(O)), 140.51, 142.63, 143.89, 145.88 (C-F), 146.84 (Ar-
C(O)), 150.31 (C-OH). 19F NMR (CDCl3, δ, ppm): -138.2 (s, 4F, Hz, Ph), -
153.98 (s, 4F, Ph). FT-IR (ν, сm-1): 796, 908 (C-Br), 982 (C-F), 1229 (Ar-
O-Ar), 1490 (С=Саrom.), 3465 (ОН). ELSD-MS: m/z = 831 [M+ 1]+.
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24
Caption for the Schemes
Scheme 1. Synthesis of fluorinated allyl- and acetyl-containing monomers.
Scheme 2. Synthesis of brominated monomers 11 and 12.
Legend for the Figures
Figure 1. IR spectra of compounds 3 - 12.
Figure 2. 1Н NMR spectra of monomer 5 (I - in CDCl3, II - in Me2SO) and
monomer 6 (III - in CDCl3).
1
Figure 3. H NМR spectra of compounds 7 and 9 obtained after various
duration of the reaction.
Figure 4. 13C NMR spectra of compounds 7 (I) and 9 (II).
Page 24 of 33

F
F
HO
O
O
OH
n
F
F
1, 2
Br
O
O
O
F
F
O
O
F
F
H3C
O
O
O
O
O
O
O
O
n
n
CH3
F
F
F
F
3, 4
7, 8
AICI3
F
O
F
F
H3C
HO
F
HO
O
O
OH
O
O
OH
CH3
n
n
F
F
F
F
5, 6
9, 10
O
n=1: 1, 3, 5, 7, 9; n=2: 2, 4, 6, 8, 10.
Scheme 1
Page 25 of 33

2
F
F
Br
Br
F
F
Br
Br
Br2
HO
O
O
OH
HO
O
O
OH
n
n
F
F
1, 2
F
F
11, 12
n=1: 1, 11; n=2: 2, 12.
Scheme 2.
Page 26 of 33

3
12
11
10
9
8
7
6
5
4
3
3500
3000
1500
1000
500
-1
Wavenumbers (cm )
Figure 1
Page 27 of 33

4
Figure 2
Page 28 of 33

5
d
a
CH3
F
F
c
O
F
F
OH
O
e
O
CDCI
d
3
eHO
O
b
CH3
c
a
b
9 (10 h)
9 (8 h)
9 (6 h)
*
*
*
*
*
*
*
*
c
F
b
a
F
O
CH3
O
a
O
b
c
O
H3C
O
F
O
F
7
M
P
P
MP 11.8
2.6
6.6
2.4
6.4
7.6
11.6
7.4
11.4
7.2
11.2
7.0
6.8
12.0
P
ppm
Figure 3
Page 29 of 33