A facile and efficient synthesis of new fluoroalkylsulfonates and the corresponding tetrabutylammonium salts

Article abstract of DOI:10.1016/j.tetlet.2019.150966

A useful synthetic methodology towards new fluoroalkylsulfonates was developed. Grignard addition to an inexpensive and commercially available fluorine-containing ester, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (1) gave the mono-adduct (2) as the only product in high yield. The scope and limitation of this method were thoroughly investigated and it was found that it works for most Grignard reagents except electron-poor ones. Interestingly, the resulting fluoroalkylsulfonates exhibit substituent-dependent hydration behavior due to the presence of carbonyl group in these compounds. Converting the fluoroalkylsulfonate to the acid form and then neutralizing it with tetra-n-butylammonium hydroxide gave the corresponding tetra-n-butylammonium salts, which shows good solubility in common organic solvents, some of which might be suitable for copolymerization with other hydrophobic monomers.

Full text of DOI:10.1016/j.tetlet.2019.150966

Accepted Manuscript
A Facile and Efficient Synthesis of New Fluoroalkylsulfonates and the Corre-
sponding Tetrabutylammonium Salts
Youbing Mu, Xiaobo Wan
PII:
S0040-4039(19)30717-8
https://doi.org/10.1016/j.tetlet.2019.150966
150966
DOI:
Article Number:
Reference:
TETL 150966
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
22 June 2019
18 July 2019
19 July 2019
Please cite this article as: Mu, Y., Wan, X., A Facile and Efficient Synthesis of New Fluoroalkylsulfonates and the
Corresponding Tetrabutylammonium Salts, Tetrahedron Letters (2019), doi: https://doi.org/10.1016/j.tetlet.
2019.150966
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Graphical Abstract
New fluoroalkylsulfonate and the corresponding tetra-n-butylammonium salt were synthesized from the
inexpensive and commercially available fluorine-containing ester, methyl 2,2-difluoro-2-
(fluorosulfonyl)acetate (1), by way of nucleophilic addition of Grignard reagents.
A Facile and Efficient Synthesis of New
Fluoroalkylsulfonates and the
Leave this area blank for abstract info.
Corresponding Tetrabutylammonium Salts
Youbing Muab, Xiaobo Wanab*

1
Tetrahedron Letters
journal homepage: www.elsevier.com
A Facile and Efficient Synthesis of New Fluoroalkylsulfonates and the Corresponding
Tetrabutylammonium Salts
Youbing Mua, b and Xiaobo Wana, b,

aKey Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, School of Chemical and Environmental Engineering, Jianghan
University, Wuhan 430056, Hubei, P.R. China.
bQingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, Shandong, P. R. China.
———
ARTICLE INFO
ABSTRACT
 Corresponding author. e-mail: wanxb@jhun.ac.cn
Article history:
Received
Received in revised form
Accepted
A useful synthetic methodology towards new fluoroalkylsulfonates was developed. Grignard
addition to an inexpensive and commercially available fluorine-containing ester, methyl 2,2-
difluoro-2-(fluorosulfonyl)acetate (1) gave the mono-adduct (2) as the only product in high
yield. The scope and limitation of this method were thoroughly investigated and it was found
that it works for most Grignard reagents except electron-poor ones. Interestingly, the resulting
fluoroalkylsulfonates exhibit substituent-dependent hydration behavior due to the presence of
carbonyl group in these compounds. Converting the fluoroalkylsulfonate to the acid form and
then neutralizing with tetra-n-butylammonium hydroxide gave the corresponding tetra-n-
butylammonium salts, which shows good solubility in common organic solvents, some of which
might be suitable for copolymerization with other hydrophobic monomers.
Available online
Keywords:
Grignard reagents
Methyl 2,2-difluoro-2-(fluorosulfonyl)acetate
Fluoroalkylsulfonate
Quaternary ammonium sulfonate compounds
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Polymers with pendant sulfonate groups have been of
significant interest both in academia and industry for many years.
They have been used to fabricate membranes for proton exchange
membrane fuel cells, water purification, and electroactive
actuators,[1] or used as template for metal nanoparticles and
inorganic/organic hybrid materials[2] or as additives to improve
the toughness of thermoplastics.[3] More attention has been paid
to those polymers with pendant fluoroalkylsulfonate groups due
to their unique physical and chemical properties.[4] The
traditional postpolymerization sulfonation method, however, is
not applicable to incorporate the pendant fluoroalkylsulfonate
groups into polymers. A commonly used approach is to directly
copolymerize monomers containing pendant fluoroalkylsulfonate
groups. A most famous example is Nafion, synthesized by the
radical copolymerization of tetrafluoro-ethylene with monomer
Ⅰ(Figure 1), a sulfonyl fluoride-substituted perfluorovinyl
ether. However, these perfluorinated vinyl ethers are costly and
can only be polymerized by free radical polymerziation with a
limited range of comonomers.[5] One alternative method to
Figure 1. Perfluorinated vinyl ethers and various types of substituted
ammonium sulfonate monomer
On the other hand, most commercially available sulfonate
monomers are in the acid or alkali salt form which endows them
with the ability to copolymerize with other polar monomers.
However, their poor solubility in organic solvents limit their
copolymerization with
a
wider range of hydrophobic
monomers.[8] To overcome these drawbacks, these monomers
could be either converted to the corresponding sulfonate esters,
which requires the use of water sensitive sulfonyl chlorides or
photosensitive silver salts,[9] or to exchange the counterion to a
more hydrophobic one.[10] The later is no doubt the more
economic route. Actually, various types of tetra-n-
butylammonium salts are used as monomers, such as monomer
II,[10g] III, [10f] IV, [11] V[10e, 10h] and VI[12] (Figure 1), which have
been polymerized by traditional/living radical polymerization
methods and successfully applied for advanced materials.
reduce the cost of polymer electrolytes is to use partially
[4b, 6]
fluorinated hydrocarbons
such as styrenic monomers with a
pendant fluoroalkylsulfonate group, which is readily polymerized
with a wide variety of comonomers under various conditions
such as anionic, cationic, coordination, and controlled radical
polymerization.[5a] So far, only a few aromatic compounds with
the pendant fluoroalkylsulfonate groups have been reported. [7]
We now wish to report an effective method for the synthesis
of a series of fluoroalkylsulfonates (2) via Grignard reaction with
an inexpensive and commercially available fluorine-containing
ester, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (1), including
the polymerizable monomer 2a.The scope and limitation of the
this method is thoroughly screened, which shows a wide-range
viability. Furthermore, a hydration equilibrium on the carbonyl
group in these magnesium fluoroalkylsulfonates in aqueous

2
Tetrahedron
solution is observed, which is strongly dependent on the
The electron-withdrawing sulfonyl fluoride group may also
contribute to the stabilizing effect.
substituent next to it. These fluoroalkylsulfonates could be
converted quantitatively to the corresponding tetra-n-butyl-
ammonium salts, some of which should be suitable for
polymerization with hydrophobic monomers.
We have shown that 2a and 2b could be synthesized in a
previous patent,[7b] and now to validate the effectiveness of above
method, we extended this methodology to other Grignard
reagents to test the scope and limitations of this reaction, and the
results are summarized in Table 2. Briefly, as shown in Table 2
(entry 1 to 4), the bromide Grignard reagents gave higher yield
than chloride Grignard reagents. Furthermore, the electronic
nature of the substituents on the para position of phenyl rings has
a profound effect on the yield. The introduction of electron
donating group slightly decreased the yield. With TBSO-, the
yield was 75% (2c) while for CH3-, the yield was 67% (2f). The
introduction of strong electron-withdrawing group at para
position inhibited the reaction (2g). Vinylmagnesium bromide
was also tested (2h), however, a large amount of unidentified
mixture was obtained, which might be due to the instability of the
resulting easily-accessible and highly reactive α,β-unsaturated
ketone which is vulnerable towards nucleophilic attack.
Switching to allylmagnesium bromide led to a pure product
which is identified to be the isomerized product (2i).
The isomerization is driven by the formation of a more stable
α,β-unsaturated ketone, and the terminal methyl group endows
steric hinderance to the alkene which protect it from
decomposition (Scheme 2). For the saturated alkyl Grignard
reagents, 2j or 2k was isolated as the major product in >60%
yield. Compound 2 series have good solubility in water and the
pH value of the solution is neutral, indicating that they are salts.
In order to confirm the counter cation, the Energy Dispersive
Spectrometry (EDS) technique was employed and the results
showed that the cation is magnesium ion.
2. Results and discussion
Esters with fluorinated α-carbon have been demonstrated to be
useful substrates to construct the corresponding ketones by low
temperature reaction (-80 oC) with Grignard reagents.[13]
However, except for trifluoroacetate, other esters with fluorinated
α-carbon still suffer from bis-addition and reduction side
products.[13] For example, addition of PhMgBr to n-C3F7CO2Et
produces 1,1-diphenyl-perfluorobutan-1-ol almost exclusively.
[13a]
Reduction product sometimes dominates when THF is used
as the solvent.[13b] We investigated in detail the addition reaction
of 1 with (4-vinylphenyl)magnesium bromide under various
conditions. Surprisingly, a 1,1-difluoro-2-oxo-ethanesulfonate
salt 2a, was formed exclusively in a yield higher than 79% under
all the experimental conditions (Table 1). It is found that No
bisadduct or reductive products were found even when excess
Grignard reagent was used (entry 3, Table 1). The results also
show that unlike the reported case,[13b] different reaction medias
have no obvious influence on the yield.
Table 1. Reaction of (4-vinylphenyl)magnesium bromide with
methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (1)
MgBr
1)
O
O
O
O
S
O
O
-80oC, 1h
H3C
S
O
F
O-
2) 0oC, aqueous workup
F
F
F F
1
2a
Entry
nGa/n1
Solventb
Isolated yield (%)
Table 2. The reaction of methyl 2,2-difluoro-2-(fluorosulfonyl)
acetate (1) with different Grignard reagents
1
2
3
4
5
6
1.1:1
1.5:1
2:1
THF(THF)
THF(THF)
THF(THF)
Tol(THF)
Tol(THF)
Et2O(THF)
82
86
86
81
84
79
O
O
O
O
O
O
R
MgX
2+
H3C
S
S
R
O
F
O-
2Mg
1.1:1
1.5:1
1.1:1
F
F
F F
2
1
Entry
RMgX
Product
2a
Isolatedyield (%)
a G was used for the abbreviation of Grignard reagent.
b In the parenthesis was shown the solvent for the Grignard reagent.
MgCl
MgBr
1
2
3
4
5
6
70
86
68
90
75
73
2a
X
Mg
O
O
S
O
O
S
O
O
O
S
O
O
S
O
O
F
R
R
- MgX(OCH3)
H2O
MgX
O
F
MgCl
MgBr
2b
H3C
O-
R
R
O
F
OCH3
F
F
F
F
F
F
F
F
2b
1
2
2'
Scheme1. The reaction mechanism of methyl 2,2-difluoro-2-
(fluorosulfonyl)acetate (1) and Grignard reagents
TBSO
MgBr
MgBr
2c
H3CO
O
2d
All these evidences indicate that the FSO2CF2- group plays an
important role in stabilize the tetrahedron addition intermediate,
as the reaction mechanism proposed in Scheme 1. We assume
that the Grignard reagents RMgX would initiate this
transformation by the nucleophilic attack at the ester carbonyl
carbon atom of 1 to furnish the tetrahedral intermediate. Besides
the electron-withdrawing effect of the difluoromethine group, [13]
the tetrahedral intermediate is also stabilized by the chelation of
the magnesium by both the oxygen atom originally belong to the
carbonyl group and the oxygen atom on the sulfonate group,
which prohibits the collapse of intermediates (2′) thus avoids the
reformation of the carbonyl group and further addition that leads
to bisadduct. Thus, upon aqueous workup, it could smoothly
yield ketone by releasing MgX(OCH3) and the hydrolysis of the
sulfonyl fluoride group leads to the final fluoroalkylsulfonate (2).
7
2e
71
MgBr
O
8
9
H3C
MgBr
MgBr
2f
67
-
2g
F3C
10
11
12
2h
2i
-
MgBr
MgBr
MgBr
MgBr
77
69
2j
13
2k
65
3

3
Br
Mg
Table 3. The equilibrium constant of 2 and its hydrate
O
O
S
O
OH
O
O
O
O
S
O
O O
O
O
S
O
O
F
H2O
HO
MgBr
S
O-
S
H3C
H3CO
O-
O-
O
F
R
R
F
F
F
F
K1[H2O]
F
F
F
F
F
F
2
3
isomerization
O
O
O
O
O
O
S
S
K [H O]
O-
O-
Entry
R
1
2
F
F
F
F
1
2
0.51
Scheme 2. Isomerization process of 2i
Like p-nitrobenzadehyde and 3-fluoroacetophene, the
carbonyl group on compound 2 could be hydrated in the presence
of water due to the electron withdrawing ability of the adjacent
RF.[14] The hydrated product coexists with the unhydrated one,
0.30
0.12
0.08
H3C
3
4
H3CO
O
1
1
which could be verified by the H NMR spectra. Typical H
NMR spectra in different deuterated solvents are shown in Figure
2, using 2a as the example. In D2O, two different sets of peaks
were observed. The peaks a, b and c are assigned to the three
protons on the double bond of 2a in the D2O (Figure 2A) and
DMSO-d6 (Figure 2B). The peaks at 6.7 ppm (c′), 5.8 ppm (b′)
and 5.3 ppm (a′) are assigned to the three protons on the
double bond of the hydrate in the D2O, while these peaks were
not found in the DMSO-d6. This difference indicates that there
exists a balance between 2a and its hydrate. Hydration was
further confirmed by high resolution mass spectrum, where the
molecular ion peak at 293.0273 is assigned to the methanol
adduct (Figure 3). Other products (2b-f and 2i-k) were also tested
and the equilibrium constant (K1[H2O]) was calculated by the
5
6
0.06
0.00
O
TBSO
7
8
0.00
0.16
9
0.16
3
Table 4. The scheme and yield of neutralization with tetra-n-
butylammonium hydroxide
O
O
O
O
O
O
1) H+ ion exchange
S
S
O-
O
R
R
2) aq. (n-Butyl)4NOH
F
F
F F
1
N(n-Butyl)4
integral of hydrate in the H NMR spectrum. The results are
2a-f 2i-k
,
4
shown in Table 3. For 2b-f, the equilibrium constant was found
to be dependent on the electronic nature of the para substituents
on the phenyl rings. With the substituent’s electron-donating
capacity increasing in the order of H-, CH2=CH-, CH3-, CH3O-,
O
2a-f, 2i-k
R
4
Isolated
yield (%)
Entry
R1
1
2
R1=R (4a)
R1=R (4b)
HO
99
98
O
and TBSO-, the equilibrium constant decreased from
TBSO
3
4
5
6
98
98
97
98
0.51 to zero. The equilibrium constant of the saturated alkyl
substituent was 0.16 and did not change with the increase of
chain length. Interestingly, in the presence of vinylic substituent,
no hydrate could be found and the equilibrium constant was zero.
(4c1)
(4e1)
H3CO
O
R1=R(4d)
O
H
O
H3C
R1=R(4f)
7
8
R1=R(4i)
R1=R(4j)
99
98
9
R1=R(4k)
99
3
Although compound 2 series show excellent solubility in
highly polar solvents such as water, dimethyl sulfoxide (DMSO)
and N,N-dimethylformamide (DMF), they exhibit very low
solubility in acetone, tetrahydrofuran (THF) and methanol. This
limited solubility would restrict its application. Thus, in order to
improve the solubility, the fluoroalkylsulfonates were converted
to the acid form and subsequently neutralized with tetra-n-
butylammonium hydroxide aqueous solution. To our delight,
white precipitates were easily obtained from the aqueous solution
and separated by filtration in almost quantitative yield (Table 4).
Figure 2. 1H NMR spectra of 2a in D2O (A) and DMSO-d6 (B)
1
A typical H NMR spectrum confirmed that the solid was the
pure quaternary ammonium sulfonate product (4a), using 2a as
the example (Figure 4). The peaks a, b, c, d and e are assigned to
the protons on the styryl group of 4a, and the peaks f, g, h and i
are assigned to the protons on the n-butyl group of 4a. The
integrals of this two group protons match well, indicating that
pure ammonium fluoroalkylsulfonates have been obtained. It
should be noted that, due to the instability of TBS group (2c) and
acetal group (2e) under the acid conditions, the 2c and 2e should
be deprotected to give the phenol and formaldehyde before
neutralization. Just like the lipophilicity of other reported
monomers with tetra-n-butylammonium cation, compound 4
series are readily soluble in a wide range of solvents including
Figure 3. The mass spectrum of 2a in methanol

4
Tetrahedron
5822; (c) Wang, X. L.; Oh, I. K.; Kim, J. B. Compos. Sci. Technol.
2009, 69, 2098-2101; (d) Hickner, M. A.; Ghassemi, H.; Kim, Y. S.;
Einsla, B. R.; McGrath, J. E. Chem. Rev. 2004, 104, 4587-4612; (e)
Nakahata, R.; Yusa, S. Langmuir 2019, 35,1690-1698; (f) Miyake, J.;
Taki, R.; Mochizuki, T. Shimizu, R.; Akiyama, R.; Uchida, M.;
Miyatake, K. Sci. Adv., 2017, 3, 35795-35800; (g) Zhang, X.; Dong,
T.; Pu, Y.; Higashihara, T.; Ueda, M.; Wang, L. J. Phys. Chem. C
2015, 119, 34, 19596-19606.
chloroform, benzene, acetone, anisole, tetrahydrofuran, N,N-
dimethylformamide, N-methyl-2-pyrrolidone and methanol at
room temperature at a high concentration (>500 mg/mL), which
makes 4a and 4i copolymerizable with a wider range of
hydrophobic monomers.
2.
3.
4.
(a) Mauritz, K. A.; Mountz, D. A.; Reuschle, D. A.; Blackwell, R. I.
Electrochim. Acta 2004, 50 ,565-569; (b) Rajan, G. S.; Mauritz, K. A.;
Stromeyer, S. L.; Kwee, T.; Mani, P.; Weston, J. L.; Nikles, D. E.;
Shamsuzzoha, M. J. Polym. Sci. Pol.Phys. 2005, 43, 1475-1485.
(a) Yao, H.; Zhang, Y.; Liu, Y.; You, K.; Song, N.; Liu, B.; Guan, S. J.
Membrane Sci. 2015, 480, 83-92; (b) Hu, Z.; Yin, Y.; Chen, S.;
Yamada, O.; Tanaka, K.; Kita, H.; Okamoto, K. J. Polym. Sci. Pol.
Chem. 2006, 44, 2862-2872.
(a) Meyer, W. H. Adv. Mater. 1998, 10, 439-448; (b) Dimitrov, I.;
Jankova, K.; Hvilsted, S. J. Fluorine Chem. 2013, 149, 30-35; (c)
Kreuer, K. D. J. Membrane Sci. 2001, 185, 29-39; (d) Mauritz, K. A.;
Moore, R.B. Chem. Rev. 2004, 104, 4535-4586; (e) Yoshimura, K.;
Iwasaki, K. Macromolecules 2009, 42, 9302-9306.
Figure 4. 1H NMR spectrum of 4a in CDCl3
5.
6.
(a) Feiring, A. E.; Wonchoba, E. R. J. Fluorine Chem. 2000, 105, 129-
135; (b) Eftekhari, A.; Saito, T.; Eur. Poly. J. 2017, 90, 245-272.
(a) Inzelt, G.; Pineri, M.; Schultze, J. W.; Vorotyntsev, M. A.
Electrochim. Acta 2000, 45, 2403-2421; (b) Kerres, J. A. J. Membrane
Sci. 2001, 185, 3-27.
3. Conclusion
As described above, we have investigated the addition
reaction of Grignard reagents to an inexpensive and
commercially available substrate 1 which led to the formation of
a series of fluoroalkylsulfonate 2 in high yield, including
monomer 2a for suitable for polystyrenic super acid. The
neighboring sulfonyl group may play a vital role in controlling
the reaction, in which its participation in the chelation of
magnesium salt prohibits the collapse of the tetrahedron
intermediate, avoiding the bisadduct and reduction side product
that is normally observed in the Grignard addition to esters with
fluorinated α-carbon. Most electron-rich Grignard regents give
good yield, while electron-poor Grignard regent does not work.
We also observed that the carbonyl moiety on the product exists
in an equilibrium with its hydrated form in aqueous solutions, the
extent of which is strongly dependent on the electron-donating
character of the substituent next to the carbonyl group.
Subsequently, converting the adducts to the acid form and then
neutralizing them with tetra-n-butylammonium hydroxide in
aqueous solution gave the corresponding tetra-n-butylammonium
salts 4 quantitatively, which shows good solubility in common
organic solvents. Currently, an effort is underway to study the
polymerization of the corresponding monomers and the
applications for advanced materials. These results will be
reported in due course.
7.
8.
(a) Toulgoat, F.; Langlois, B. R.; Médebielle, M.; Sanchez, J. Y. J.
Org. Chem. 2007, 72, 9046-9052; (b) J. T. Goldbach, X. Wan, D. A.
Mountz, WO-2012-018709.
(a) Bouix, M.; Gouzi, J.; Charleux, B.; Vairon, J. P.; Guinot, P.
Macromol. Rapid Comm. 1998, 19, 209-213; (b) Oikonomou, E. K.;
Pefkianakis, E. K.; Bokias, G.; Kallitsis, J. K. Eur. Polym. J. 2008, 44,
1857-1864; (c) Oikonomou, E. K.; Bethani, A.; Bokias, G.; Kallitsis, J.
K. Eur. Polym. J. 2011, 47, 752-761.
(a) Emmons, W. D.; Ferris, A. F. J. Am. Chem. Soc. 1953, 75, 2257-
2257; (b) Okamura, H.; Takatori, Y.; Tsunooka, M.; Shirai, M.
Polymer 2002, 43, 3155-3162; (c) Baek, K.Y. J. Polym. Sci. Pol.
Chem. 2008, 46, 5991-5998; (d) Mori, H.; Saito, Y.; Takahashi, E.;
Nakabayashi, K.; Onuma, A.; Morishima, M. Polymer 2012, 53, 3861-
3877; (e) Lienkamp, K.; Ruthard, C.; Lieser, G.; Berger, R.; Groehn,
F.; Wegner, G. Macromol. Chem. Phys. 2006, 207, 2050-2065.
9.
10. (a) Lundberg, R. D.; Thaler, W. A.; Turner, S. R. 1985, US4552939 A;
(b) Kertes, A. S.; Inorg. J. Nucl. Chem. 1965, 27, 209-217; (c)
Yoshizawa, M.; Ogihara, W.; Ohno, H. Polym. Advan. Technol. 2002,
13, 589-594; (d) Ohno, H.; Yoshizawa, M.; Ogihara, W. Electrochim.
Acta 2004, 50, 255-261; (e) Ricks-Laskoski, H. L.; Snow, A.W. J. Am.
Chem. Soc. 2006, 128, 12402-12403; (f) Liu, Y.; Pollock, K.L. ;
Cavicchi, K.A. Polymer 2009, 50, 6212-6217; (g) Pitia, E.; Shaw,
M.T.; Weiss, R. A. Polymer 2011, 52, 297-306; (h) Prescher, S.;
Polzer, F.; Yang, Y.; Siebenburger, M.; Ballauff, M.; Yuan, J. J. Am.
Chem. Soc. 2014, 136, 12-15.
11. McCullough, L.A.; Dufour, B.; Matyjaszewski, K. J. Polym. Sci. Pol.
Chem. 2009, 47, 5386-5396.
12. (a) Gao, L.; Johnston, D.; Lonergan, M.C. Macromolecules 2008, 41,
4071-4080; (b) Robinson, S. G.; Johnston, D. H.; Weber, C. D.;
Lonergan, M. C. Chem. Mater. 2009, 22, 241-246.
Acknowledgments
13. (a) Creary, X. J. Org. Chem. 1987, 52, 5026-5030; (b) Yamazaki, T.;
Terajima, T.; Taskasuka, T. K. Tetrahedron, 2008, 64, 2419-2424.
14. (a) Sayer, J. M. J. Org. Chem. 1975, 40, 2545-2547; (b) McDonald, R.
S.; Teo, K. C.; Stewart, R. J. Chem. Soc. Perk. T. 1983, 2, 297-299.
This work was supported by the National Science Foundation
of China (51603223).
References and notes
Click here to remove instruction text...
1.
(a) Dunwoody, D.; Leddy, J. J. Electrochem. Soc. Int. 2005, 14, 37-39;
(b) Geise, G. M.; Freeman, B. D.; Paul, D. R. Polymer 2010, 51, 5815-

5
Highlights




New fluoroalkylsulfonates were synthesized by
Grignard addition reaction.
The sulfonyl group helps to stabilize the
tetrahedron intermediate to avoid side reactions.
The hydration behavior of fluoroalkylsulfonate
was studied.
Tetra-n-butylammonium fluoroalkylsulfonates
were easily prepared quantitatively..