Synthesis and characterization of fluorinated bisphenols and tetraphenols via a simple one-pot reaction

Article abstract of DOI:10.1080/00397911.2012.705214

Fluorinated bisphenols and tetraphenols have been prepared by the condensation reaction of trifluoromethyl activated ketones with simple bisphenols (including catechol, resorcinol, and hydroquinone) catalyzed by trifluoromethanesulfonic acid, in good yields. Copyright

Full text of DOI:10.1080/00397911.2012.705214

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Synthesis and Characterization of
Fluorinated Bisphenols and Tetraphenols
via a Simple One-Pot Reaction
Liming Tao a b , Haixia Yang b , Jingang Liu b , Lin Fan b & Shiyong
Yang b
a State Key Laboratory of Solid Lubrication, Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences , Lanzhou , China
b Laboratory of Advanced Polymer Materials, Institute of Chemistry,
Chinese Academy of Sciences , Beijing , China
To cite this article: Liming Tao , Haixia Yang , Jingang Liu , Lin Fan & Shiyong Yang (2013): Synthesis
and Characterization of Fluorinated Bisphenols and Tetraphenols via a Simple One-Pot Reaction,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 43:17, 2319-2325
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Synthetic Communications1, 43: 2319–2325, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2012.705214
SYNTHESIS AND CHARACTERIZATION OF
FLUORINATED BISPHENOLS AND TETRAPHENOLS
VIA A SIMPLE ONE-POT REACTION
Liming Tao,1,2 Haixia Yang,2 Jingang Liu,2 Lin Fan,2 and
Shiyong Yang2
1State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical
Physics, Chinese Academy of Sciences, Lanzhou, China
2Laboratory of Advanced Polymer Materials, Institute of Chemistry, Chinese
Academy of Sciences, Beijing, China
GRAPHICAL ABSTRACT
Abstract Fluorinated bisphenols and tetraphenols have been prepared by the condensation
reaction of trifluoromethyl activated ketones with simple bisphenols (including catechol,
resorcinol, and hydroquinone) catalyzed by trifluoromethanesulfonic acid, in good yields.
Supplemental materials are available for this article. Go to the publisher’s online edition
of Synthetic Communications1 to view the free supplemental file.
Keywords Fluorinated bisphenols and tetraphenols; hydroxyalkylation reaction;
superacid
INTRODUCTION
The hydroxyalkylation reaction of the superacid-catalyzed condensations of
aldehydes and ketones with arenes has been studied by Kray[1] and O’Connor[2]
et al. This reaction has an important role in polymer chemistry, as it is the reaction
Received March 17, 2012.
Address correspondence to Shiyong Yang or Haixia Yang, Laboratory of Advanced Polymer
Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China. E-mail: shiyang@
iccas.ac.cn; yanghx@iccas.ac.cn
2319

2320
L. TAO ET AL.
Scheme 1. Sythesis of 6FDA.
used to make bisphenols and many condensation polymers derived from phenols.
This laboratory has recently been interested in various fluorine-containing func-
tional monomers that can be used in preparing high-performance heteroaromatic
polymers (HAPs), such as polyimides (PIs),[3] polyarylethers (PAEs), and polyben-
zoxzoles (PBOs)[4] as low dielectric constant materials. The trifluoromethyl (–CF3)
group is the most prominent representative in the series of perfluoro alkyl group.
Introduction of –CF3 groups in the polymer structure has been one of the most
widely used strategies[5,6] to obtain solution processable polymers with a desired
set of properties.
It is known that in trifluoromethanesulfonic acid (TFSA), carbonyl com-
pounds containing electron-withdrawing groups can form highly reactive intermedi-
ates that are capable of subsequent transformations.[7–10] In this superacid medium,
arylation of activated ketones can be carried out smoothly, which does not take
place under conditions of conventional acid catalysis. For instance, 2,2,2-trifluoroa-
cetophenone (3FK) and its derivatives react with toluene in the presence of TFSA,
whereas acetophenone is inert under these conditions.[1,9] This reaction has been
widely used in the synthesis of functional monomers such as diamines, dianhydrides,
bisphenols, and trisphenols, which are used in the synthesis of high-performance
polymers. For example, the most used fluorinated dianhydrides 4,4-(hexafluoroiso-
propylidene)diphthalic anhydride (6FDA) and the most used fluorinated bisphenol
2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPA-F) can be prepared by using this
reaction, according to Schemes 1 and 2, respectively. Recently, this chemistry has
been applied directly to the synthesis of several novel condensation polymers by
Zolotukhin et al.[11–17]
In the hydroxyalkylation reaction, the arene reactant that had been most
studied contains the benzene,[2] phenol,[4] toluene, aniline,[1] o-xylene,[18] anisole,[19]
and so on. The trifluoromethyl activated ketones contain 2,2,2-trifluoroacetophenone
(3FK), 30-trifluoromethyl-2,2,2-trifluoroacetophenone (6FK), and 30,50-ditrifluoro-
methyl-2,2,2-trifluoroacetophenone (9FK), the structures of which are presented in
Scheme 3. However, the reactions of trifluoromethyl activated ketones with the three
kinds of simple bisphenols (catechol, resorcinol, and hydroquinone) have not been
reported untill now. As part of our investigations on the synthesis of novel fluorinated
polyfunctional monomers, we further investigated these reactions and in this
Scheme 2. Synthesis of BPA-F.

FLUORINATED BISPHENOLS AND TETRAPHENOLS
2321
Scheme 3. Structures of the trifluoromethyl activated ketones and bisphenols used in the present article.
Scheme 4. Synthesis of the fluorinated tetraphenols.
communication we report a convenient method for the preparation of the previously
unreported tetraphenols and bispheonls as shown in Schemes 4 and 5. Thus, treat-
ment of three kinds of ketones (3FK, 6FK, and 9FK) with three kinds of bisphenols
(catechol, resorcinol, hydroquinone) in dichloromethane (DCM) yielded unexpect-
edly the fluorinated bisphenols and tetraphenols (1–9, Table 1) as major products,
respectively, along with minor amounts of by-products. The nomeculature of the nine
products followed the ketones’ names (3FK, 6FK, and 9FK) and the bisphenols (cat-
echol, resorcinol, and hydroquinone); for instance, 3F-C is the product derived from
3FK and catechol.
Scheme 5. Synthesis of the fluorinated bisphenols.

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L. TAO ET AL.
Table 1. Preparation of fluorinated bisphenols and tetraphenols
Reactant A
Reactant B
Conditionsa
Ratio A:B Product Yieldb (%) Mp (ꢀC)
3FK
Catechol
TFSA (0.25 equiv to B),
DCM, rt, 4 h
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
3F-C
3F-R
3F-H
6F-C
6F-R
6F-H
9F-C
9F-R
9F-H
80
85
90
78
80
87
81
90
89
199
190
210
173
183
222
164
209
180
Resorcinol
TFSA (0.25 equiv to B),
DCM, rt, 8 h
Hydroquinone TFSA (0.25 equiv to B),
DCM, rt, 8 h
6FK
9FK
Catechol
TFSA (0.25 equiv to B),
DCM, rt, 8 h
Resorcinol
TFSA (0.25 equiv to B),
DCM, rt, 8 h
Hydroquinone TFSA (0.25 equiv to B),
DCM, rt, 8 h
Catechol
TFSA (0.25 equiv to B),
DCM, rt, 8 h
Resorcinol
TFSA (0.25 equiv to B),
DCM, rt, 8 h
Hydroquinone TFSA (0.25 equiv to B),
DCM, rt, 8 h
aReaction conditions were not optimized;
bYields were not optimized.
RESULTS AND DISSCUSSION
The catalyst used here was also TFSA. The ketone and the bisphenol (the
molar ratio of ketones to catechol was fixed to be 1:2) along with DCM were placed
into the flask. Under mechanical stirring and nitrogen flow, TFSA was dropped into
the reaction mixture slowly. The color turned light red as the first drop of TFSA was
added to the mixture. Then the mixture color became darker gradually. The mixture
was stirred for about 4 to 8 h at room temperature. The precipitated crude product
was then collected, washed with hot water several times, and vacuum dried.
When catechol was used to react with the activated ketones, tetraphenols were
obtained without any by-products. The structures of the three kinds of tetraphenols
were characterized in detail.
On the other hand, when resorcinol and hydroquinone were used to react
with the ketones, tetraphenols were not obtained as expected, but dehydration pro-
ducts (fluorinated bisphenols with dibenzopyran ring) were obtained instead in all
cases.
We believe that the mechanism of this reaction of resorcinol and 3FK can be
illustrated in Scheme 6. When catechol was used, the final dehydration step should
be difficult because of the steric factors; therefore, the tetraphenols were obtained
as a result.
The fluorinated bisphenols and tetraphenols synthesized here can be further
transformed to a large number of functional monomers or additives as mentioned
previosly. For instance, reacted with 1,2-naphthoquinone-2-diazido-5-sulfonyl chlor-
ide, the tetraphenols can be transited to be a kind of photoresist containing four
reactive functional groups. The relative fictionalization is ongoing in this laboratory.

FLUORINATED BISPHENOLS AND TETRAPHENOLS
2323
Scheme 6. Postulated mechanism of the reaction.
CONCLUSION
In conclusion, we have developed a simple, practical, metal-free, one-pot
method for the synthesis of fluorinated bisphenol and tetraphenol derivatives with
good yields under mild conditions, by the condensation of trifluoroacetophenones
and bisphenols. Operational simplicity and the mild reaction conditions are the
advantages of the present procedure. We believe that this is a very simple and more
practical alternative to the existing methodologies for the synthesis of fluorinated
bisphenols and tetraphenols.
EXPERIMENTAL
3F-C was given as an example. A mixture of 3FK (3.482 g, 0.02 mol), DCM
(40 mL), and catechol (4.404 g, 0.04 mol) was placed into a 100-mL, three-necked,
round-bottomed flask fitted with a mechanical stirrer, nitrogen inlet, and a dropping
funnel. Then, TFSA (1.5 g, 0.01 mol) was added dropwise at room temperature for
about 10 min. The mixture was stirred for another 4 h in nitrogen. Then the precipi-
tate was collected by filtration and washed with boiling water and DCM successively.
The light-red crude product obtained was purified by recrystallization in ethanol to
afford pale white powders of 6.0 g (yield: 80%; mp: 199 ꢀC by DSC in N2, 10 ꢀC=min).
All the other products were prepared according to a similar procedure and
were characterized by their spectral and analytical data (see Supplementary Infor-
mation, available online, for details).
ACKNOWLEDGMENT
Funding from National Natural Science Foundation of China is gratefully
acknowledged (Nos. 51103168 and 50903087).

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L. TAO ET AL.
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