Journal of Industrial and Engineering Chemistry 31 (2015) 2638

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Review

Ionic liquids based uorination of organic compounds using

electrochemical method
Zia Ul Haq Khan a, Dondan Kong a, Yongmei Chen a,*, Nawshad Muhammad b,
Arif Ullah Khan a, Faheem Ullah Khan a, Kamran Tahir a, Aftab Ahmad a,
Lei Wang a, Pingyu Wan a,*
a
b

School of Science, Beijing University of Chemical Technology, Beijing 100029, PR China

Interdisciplinary Research Centre in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000, Pakistan

A R T I C L E I N F O

Article history:
Received 20 December 2014
Received in revised form 6 June 2015
Accepted 6 June 2015
Available online 20 June 2015
Keywords:
Partial uorination
Electrochemistry
Organic compounds
Ionic liquids

A B S T R A C T

Ionic liquids due to their advantageous properties gain importance in many elds. This study aims to
overview the use of ionic liquids in the selective partial uorination of organic compounds through
electrochemical method. In addition to ionic liquid based uorination, the earlier approaches of
uorination through an electrochemical process have also been highlighted. The factors such as
electrode materials (Pt, Ni, and C), types of solvents (CH3CN, DMC, THF, DME, Sulfone, etc.) and type of
electrolytes (Et3N3HF, Et3NF3HF, pyHF, etc.) which affect the electrochemical uorination of organic
compounds have been reviewed. For electrode preparation, the carbon, platinum and nickel were
considered suitable materials to be used as an electrode. In CH3CN media, Et3N3HF and Et4NF3HF
showed better efciency during uorination of organic compounds. Solvent play an important role in
electrochemical uorination of organic compounds, with the change of solvent the percentage yield is
highly affected. Py-HF is a convenient solvent-supporting electrolyte medium with a reasonably good
conductivity. The electrolyte containing solvents have some side effects on electrochemical uorination
of organic compounds as observed in cyclic voltammetric analysis. Therefore electrochemical
uorination to organic compounds without the use of solvent gained more importance. The ionic
liquids have been reported for its dual properties, as solvent as well as a uorinating agent for organic
compounds in electrochemical processes. It has been concluded that solvents free electrochemical
uorination of organic compounds gives good results as compare to solvent based. Ionic liquids due to
more oxidative stability were noted to have considerable effect on the yield and selectivity of organic
compound uorination.
2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fluorination process . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of electrode materials on uorination process . . . .
Effect of solvents on electrochemical process . . . . . . . . .
Effect of supporting electrolytes on uorination process.

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27
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31

Abbreviations: DMC, dimethyl carbonate; THF, tetrahydrofuran; DME, dimethoxyethane; CV, cyclic voltammogram; ECF, electro chimerical uorination; ILs, ionic liquids;
PTFE-FFP, poly tetra uoro ethylene-fresh frozen plasma; HF, hydrouoric acid; ECb ECn, electrochemical; MCN, acetonitrile; Py-HF, pyridine-hydrouoric acid; DCM,
dichloromethane; ECPF, electrochemical per-uorination.
* Corresponding authors. Tel.: +86 10 64435452; fax: +86 10 64445917.
E-mail addresses: ziaulhaqkhan11@gmail.com (Z.U.H. Khan), chenym@mail.buct.edu.cn (Y. Chen), pywan@mail.buct.edu.cn (P. Wan).
http://dx.doi.org/10.1016/j.jiec.2015.06.007
1226-086X/ 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

Electrochemical peruorination (ECPF) of organic compounds . . . . . . . . . . . . . . .

Electrolytic partial uorination of organic compounds . . . . . . . . . . . . . . . . . . . . .
Ionic liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ionic liquid hydrogen uoride salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrochemical properties of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . .
Ionic liquid as uorinating agent in electrochemical uorination process.
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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27

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31
32
33
33
33
34
37
38
38

Introduction
Fluorinated organic compounds have unique properties and
especially partially uorinated organic compounds play an
important role in preparation of novel medicine [13], in the
area of agriculture [4] and also in development of functionalized
materials [5]. About 4045% of agrochemicals contained uorine
element in their compositions. Electro chimerical Fluorination
(ECF) is one of the best tools in uorination of organic compounds
that involved the conversion of CH to CF bond. Usually three
methods are used in electrochemical partial uorination to
organic compounds [610]. Among these methods, electrochemical partial uorination is very attractive because uorine atoms
can be introduced into organic molecules in one step under safe
conditions [7,11] and results in different types of new uorinated
organic compounds [1214]. General synthesis normally results
in large quantities of both inorganic and organic by-products. The
ECF is attractive methods and it is more advanced as compare to
other general methods and not accompanied by by-products
synthesis. Electrochemistry, since 50 years made a signicant
contribution in the area of uorination of organic compounds with
the development and commercialization of the Simons Process
[15]. In most case uorination process is completed in many
different ways, in which the bond between CC breaks and
subsequently rearranged with high extent, but the yield is very
poor. Electrochemical process is very friendly and not a case in the
handling of uorine gas and in several cases also conserves the
molecule functionality [16]. The ECF of organic compounds, direct
as well as indirect methods have been used. Fuchigami and his
co-worker reported electrochemical uorination of organic
compounds to dithioketals 92, by indirect method using Et4NBr
in catalytic amount and Et3N3HF was used as mediator as
uorinating agent to corresponding mono ouro thio ether 93,
and get very good result without formation of other by products
(Scheme 1) [17]. Similar results were reported by other
researchers using direct methods [17]. Ionic liquids (ILs) are
molten salts having melting point below 100 8C and are
considered as green solvent due to their advantageous properties
[18]. Ionic liquids are considered one of the best solvent in organic
syntheses, electro organic syntheses, catalysis and for polymerization [1925]. This study highlights the facile route of
electrochemical uorination of organic compounds. The factors
such as the electrode materials, solvents, electrolytes and other
additives which affect the uorination process have been
highlighted. The venture of ionic liquid for its potential application in the uorination of organic compounds has been described
in detail.

Fluorination process
Electrochemical uorination (ECF) in a-HF is generally used for
the electrochemical uorination to organic compounds. Partial
electrochemical uorination to organic compounds is useful tools
for the synthesis of new organic compounds using Simon process
in technical and laboratory level [26]. Till now the mechanism of
partial electrochemical uorination of organic compound using
Simon process are employed. Several proposals about the possible
mechanism of this process were made during the years [26] but
neither one was conrmed experimentally. Simons process takes
place at the surface of the Ni anode, covered by a NiF/NiFz-lm.
That was proved by an independent experiment as follows: 1.45 g
of CH3SO2F was treated in a PTFE-FEP vessel with 16 g of
anhydrous HF, previously electrolyzed in the Simons type
electrolytic cell during 46 h.

28

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

Scheme 1. Schematic representation of auto-ination process [26].

Scheme 2.

It is evidence from numerous experiments that during

electrochemical uorination to organic compounds, the oxidation
leads the formation of cation radical. During electrochemical
uorination, mostly side reaction takes place when the compounds
contain active methylene groups. Usually partially and selective
electrochemical uorination proceeds by ECBECN type mechanism. From the mechanism, it is clear that in the rst step uoride
attached with the benzene ring and in the second step loss of
protons takes place [27,28].
In some case to release Proton is the rst step in case SCF (side
chin uorination) [27].
Fluorination to double bonded anodic ally, different uorinated
agents and different solvents leads to this addition and led the
formation of vicinal uorinated compounds [2729]. Et3N3HF was
used for electrochemical uorination to styrene (1) as uorinated
agent and MCN was used as solvent and get Vic-diouro
compounds (2) invaluable yield. The mixture of products (1:2)
1, 2 and 1, 4 adducts, 4 and 5 will be formed respectively (Schemes
24).

Effect of electrode materials on uorination process

Carbon, platinum and nickel show very high corrosion
resistance in anhydrous HF [6]. On pt electrodes electro oxidation
due to PtF2 and PtF4 lm formation starts around 1 V and uorine
evolution occurs around 2.5 V [16,6]. Fluoride lm formation on
the carbon electrode starts around 1.5 V. However, the lm growth
and uorine generation rates are considerably higher on this
electrode. In order to investigate electrochemical uorination to
organic compounds higher binary uorides has been subjected
(Simons Process ECE) [30]. The methods give good results with the
nickel are used as an anode. Different researcher [31,10] considers
that higher nickel uorides are generated at anode during the
electrochemical uorination process. Most of researchers [3234]
are trying to synthesis higher nickel containing uoride by using
electrochemical uorinated methods. Organo-phosphorus is an
important compound. The electrochemical uorination via Simons
Process, namely of tri alkyl phosphine oxides, is reported in the
literature [34]. By this process, the corresponding tris (perfuor-

Scheme 3.

Scheme 4. The anodic uorination to double bonds [17].

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

Scheme 5.

oalkyl)difuoro phosphoranes can be obtained in a yield of 2446%

[33], Scheme 5.
Effect of solvents on electrochemical process
The best choice of solvent for selective uorination through
electrochemical method is CH3CN [16]. This solvent, however, is
not exclusive. Other solvents such as sulfolane [35], DMC [36,37],

29

DME [38,39], have also been used. Py-HF is a convenient solventsupporting electrolyte medium with a reasonably good conductivity. Hence, efforts were also made to use this medium for
selective electrochemical uorination [40]. Selective uorination
leading to the formation of heteroatom uorine bonds should also
be considered as a signicant development [41]. Solvent play
important role in electrochemical uorination of organic compounds, with the change of solvent the percentage yield is highly
affected. The yield will be twice when ethereal solvent, such THF,
DME, Dioxin, instead of MCN that are used as solvent (run 36, 10),
while DCM and DMC have no effect on the yield of products. The
effect has been studied in Table 1.
More than 10 years ago, Fuchigami and his co-worker achieved
independently anodic a-uorination of ethyl a-phenyl the acetate
(1) in Et3N3HF/MeCN [4244] (Scheme 6).

Table 1
Anodic mono uorination of alkyl phenyl suldes [40].
Run

1
2
3
4
5
6
7
8
9
10

No.

5a
5a
5a
5a
5a
5a
5a
5a
5b
5b

H
H
H
H
H
H
H
H
Me
Me

Solvent

MeCN
MeCN
THF
THF
DME
Dioxane
DMC
DMF
MeCN
THF

Anodic potential V vs. SSCE

Current density, mA/cm2

+1.6
6.3a
+3.3
6.3a
6.3a
6.3a
6.3a
+1.6
+1.8
+3.3

Charge passed, F/mol

2.1
2.0
6.1
5.0
4.5
3.0
3.0
4.0
4.0
6.1

Product yield (%)

6

23 (6a)
20 (6a)
45 (6a)
52 (6a)
57(6a)
47 (6a)
22 (6a)
5 (6a)
18(6b)
45(6b)

45
62
b
32
25
21
24
6
b
b

(7a)
(7a)
(7a)
(7a)
(7a)
(7a)
(7a)
(7a)

Scheme 6. Ref. [43].

Fig. 1. Cyclic voltammograms for the oxidation of 4 mM of C6H5SCH2COOCH3 on Pt in CH3CN (A) 0.1 M TBAP and (B) Et3N3HF at different scanning speeds (v) (mV). (a) 20, (b)
40, (c) 80, (d) 160, (e) 320, and (f) 640 [46].

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

30

Table 2
Oxidation peak potentials and peak currents of suldes contains active methylene group PhSCH2R [47].
ipal (mA cm2)

No

Sub. no

Substrate [R]

Epal (V)
TBAP/CH3CN

Et3N3HF/CH3CN

TBAP/CH3CN

Et3N3HF/CH3CN

1
2
3
4
5
6
7
8

1a
2a
3a
4a
5a
6a
7a
8a

COOMe
COOC6H4-Cl-P
CONC6H4-Cl-P
COOC6H4-NO2-P
CONH2
CONHC6H4-NO2-P
CONHC6H5
COOC6H5

1.62
1.84
1.63
1.76
1.71
1.69
1.71
1.69

1.46
1.72
1.63
1.62
1.57
1.52
1.48
1.04

3.27
2.71
1.50
2.78
1.64
1.58
1.48
3.69

4.43
3.75
3.06
2.94
2.17
2.11
2.46
1.07

Ipal rst anodic peak current, Epal anodic peak potential, S.R. = 40 mV/s, Concentration = 10 mM.

Table 3
Selective electro uorination of suldes containing active methylene groups [26].
No

Sulde

1a
2a
3a
4a
5a
6a
7a
8a

1
2
3
4
5
6
7
8
a

Sub. no

Average Cell voltage (V)

COOMe
COOC6H4-Cl-P
COOC6H4-Cl-P
COOC6H4-NO2-P
CONH2
CONHC6H4-NO2-P
CONHC6H5
COOC6H5

3.80
5.10
5.20
5.00
4.70
5.10
5.80
7.00

Product yielda

Total yield

b+c

72
12
7
6
22
6
6
17

5
56
56
50
27
36
28
10

77
68
63
56
49
42
34
27b

Un reacted substrate

14
22
5
10
14

Yield from HPLC.

Multiple peaks.

Table 4
Anodic uorination of ethyl a-(phenylthio) acetate in Et3N3HF ionic liquid with or without ultrasonication.
Yielda (%)

Current/density
2

Selectivity of 2 (%)

Run

Ultrasonication

mA cm

Total

1
2
3
4
5
6
7
8

No
Yes
No
No
Yes
No
Yes
Yes

2.5
2.5
5.0
10
10
25
25
50

79
90
54
33
85
3
65
65

8
0
21
24
4
3
8
15

86
90
75
57
89
6
73
79

Determine by

91
100
72
58
95
50
89
82

19

FNMR.

By comparison the result of MCN/TBAP and MCN/EtN3HF

showed a slightly lower anodic limit. In electrochemical uorination, while using MCN as solvent, oxidation current noticed more
than 2 V [44,45]. Cyclic Volta metric result (CV) of 1a, using
EtCNEt3N3HF system is presented in gure (B). The anodic band is
slightly more while using this solvent system (compare Figure A
and B). The potential is also being shifted to positive potential.
Compounds 2a8a in the same solvent system also showed the
same effect. In the above solvent system the potential increase
from 2 V, the 3rd anodic peak, which is not visible (compare
Fig. 1(A) and (B). The value of current and potential range for all the
eight (1a8a) compounds are summarized in Table 2. The rst step
is simple and oxidized at a lower potential, which indicate that the
oxidation process in above said (CH3CN/Et3N3HF) system is very
simple, while the peak range found to be higher in solvent system
CH3CN/TBAP, Table 4. The CV pattern is also similar [40]. Hence,
one may presume that the active site for the initial oxidation of the
reactant is the same in CH3CN/TBAP as well as CH3CN/Et3N3HF
media, namely the S atom. The results of the present study
Table 3 show that an adsorption effect can also be lower for

Scheme 7.

some compounds containing more than one phenyl group [45]

(Scheme 7).
During electrolysis, anodic uorination anodic passivation
takes place during that process. In the same electrolytic solution
the anodic uorination of compounds (1) was unsuccessful, while
uorination to a-mono acetate (2) mostly give a-di uorinated

Fig. 2. Sonovoltammogram of ethyl a-phenylthioacetate (1) in ionic liquid,

Et3N3HF [44].

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

31

Table 5
Effect of solvent in Et3N3HF on anodic uorination of organic compounds.
No

Substrate

Products yields %
MeCN

DME

DMC

DMF

1
2
3

PhSCH3a,b
(Ph)2C5
5NNH2
PhSCH2COORc

21

54

57
62

22
95
43

5
31
12

a
b
c

Main products

Reference

PhSCH2F
Ph2CHF
PhSCHFCOOR

[6]
[34]
[41]

THF yield 52%.

Dioxane yield [45].
R = 8-phenylmenthyl.

Scheme 8.

compound 3 in valuable yield by passing excess of electricity

(Scheme 2) [46]. In order to diminish that problem, to uorinated
to compounds 1, purely net Et3N3HF is used under ultrasonication
[47], as shown in Fig. 2. ILs have higher viscosity as compare to that
of other organic solvents, therefore the process is a little slower as
compared to organic solvent. The main application of ultrasonication is to generate cavitations and to generate micro-jet stream,
transport, and mass of the compound 1 to the anodic surface the
viscose ILs. From that result it is clear that Et3N3HF act likely
common solvent under ultrasonication. Fluorination of (phenyl thio)
acetate in Et3N3HF ILs or without ultrasonication and the effect of
solvent in Et3N3HF on anodic uorination of organic compounds are
summarized in Tables 4 and 5, respectively (Scheme 8).
Effect of supporting electrolytes on uorination process
As described earlier that MeCN is mostly used solvent for the
electro uorination of organic compounds. For electrochemical
uorination to organic compounds MCN is generally used as solvent.
For the sources of uorine different supporting electrolyte has been

used. Et3.NF.nHF and Et3.NF.nHF are the most commonly employed

uoride sources. Some studies have also reported pyridine-HF as
uoride source. In other investigations, the efciency of different
electrolyte in MCN, during partial electrochemical uorination was
compared, summarized in Table 2 [4852]. In CH3CN media,
Et3N3HF and Et4NF3HF showed better efciency during uorination of organic compounds. Some general guidelines seem to exit
[53] in which Et3N3HF reported to give good yield in some cases [50],
while in other Et4NF3HF have shown good [50,52,53]. The pay-HF is
considered to be acting as a poor supporting electrolyte. However,
some researchers indicate that py-HF medium is very good for
electrochemical uorination to organic compounds [52]. Effects of
supporting electrolytes in CH3CN on anodic uorination of organic
compounds are summarized in Tables 6 and 7.
Similarly to CH2Cl2 and THF as shown in Scheme 9.
Electrochemical peruorination (ECPF) of organic compounds
Per uorinated compounds play important role in articial blood
and O2 barriers [54]. An-HF are commonly used as a uorinated
reagent to convert all passable CH to CF.AHF are extremely toxic
because of low boiling point, and also the productivity is very poor.
For example ECF of N,N-DI methyl triuoro methane sulfonamide (1)
give corresponding partial ournated, N,N-bis(triuoromethyl)
peruoro alkane sulpho namide (2) along with by products 3 and
4 (Schemes 10 and 11) [55].

Table 6
Effect of supporting electrolytes in CH3CN on anodic uorination of organic compounds.
No

Substrate

Products yields %
Et3N3HF

Et4NF3HF

Py-NHF

Main product

Reference

PhSCHCF3
PhSCHFCOOEt

[49]
[47]

1
2

PhSCH2CF3
PhSCH2COOEt

62
61

61

Ph.S

77

64

Trace

4
5

PhSCH2COOR

54
56

37
72

73

[50]

80

66

[50]

[52]

PhSCHCOOR

[51]
[50]

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

32

Table 7
Solvent effect on anodic uorination of 3-phenylthiophthalide [44].
Run

Reaction

Supporting electrolyte

Charge passed (F/mol)

1
2
3
4
5
6
7

MeCN
DMC
THF
DME
[EMIM][OTf]
[EMIM][OTf]
[EMIM][BF4]

Et3N3HF
Et3N3HF
Et3N3HF
Et3N3HF
Et3N3HF
Et3N3HF
Et3N3HF

4
4
4
3
4
4
3.5

Yield (%)
A

44
86
6
9
44
83
65

22
72

Trace

Scheme 9. Ref. [44].

Electrolytic partial uorination of organic compounds

Fluoro organic compounds have rather unique chemical and
physical properties. In 1970, Rozhkov and co-workers reported the
rst successful example of anodic mono uorination of naphthalene [56,57] since then, anodic partial uorination of aromatics,
hetero aromatics, olens, and a-phenyl acetate derivatives has
been performed [58,59]. However; there has so far been no report
on anodic partial uorination of organo sulfur compounds
[10]. Historical development in the selective electrochemical
uorination of organic compounds has been summarized in Table 8
(Scheme 12).

Scheme 10.

Fuchigami and his co-workers have reported selective uorination of 4-thiazolidinones and subsequent conversion of our
thiazolidinones to our-lactams which are of pharmaceutical
importance [71,72]. Electro uorinations of b-lactams [73]

Table 8
Historical development in the selective electrochemical uorination of organic compounds [10].
Year

Subtract

Solvent, supporting,
electrolyte

Product

Yield %

Reference

1953
1955
1955

PhC5
5CH2
CH3CH2COOH
CCl25CCl2

Ph2CF-CH2F
CH2FCH2COOH
CFCl2-CFCl2

70

Trace

[60]
[61]
[62]

1960
1970

Ph2C5
5CH2

KHF2-ACOH
AHF
HF-MeCN
HF-ETOH
HF-AcOH
AgF/MeCN
Et3NHF-MeCN

Ph2CF-CH2F

4.5

[63]
[64]

1970

Et4NHF-MeCN

40

[65]

1971

Et4NHF-MeCN

12

[66]

1979

30%Py70%HF

[67]

70
50
35

[68]
[69]

1982
1984

Et2NP(OET)2
pMeOC6H4CH2CN

(EtNH2)SiF6
(Et3N3HF-MeCN)

1990

PhSCH2CF3

Et3N3HF-MeCN

(EtO)2POF
p-MeOC6H4CHCN
p-MeOC6H4CHCN
PhSCHCF3

[70]

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

33

4-thianone derivatives [46] and other heterocyclic compounds

[74] have also been reported. This class of compounds probably
would be the rst to achieve commercial success through a
selective electro uorination route.
Ionic liquid
Ionic liquids are salts that form a stable liquid near room
temperature or at 100 8C, gain signicant research interest as
environmentally benign reaction media. The majority of ILs is
derived from the combination of small cartons and weakly
coordination anions. These are quaternary ammonium, phosphonium, imidazolium, or pyridinium cations with large, chargediffuse inorganic counter ions. In these shots, the cation core has
appended to it one or more organic group. Typically, these are
saturated alkyl groups.

Scheme 11.

Electrochemical properties of ionic liquids

Ionic liquids are widely used in the selective electrochemical
uorination of organic compounds given in Tables 9 and 10. The ILs

Ionic liquid hydrogen uoride salt

Ionic liquid hydrogen uoride salts are poly hydrogen uoride
complex with quaternary ammonium, imidazolium, pyridinium
uoride. Generally, anhydrous hydrogen uoride is an uncontrollable reagent because of its low boiling point and hard corrosivity.
However, ionic liquid HF salts are easily prepared and safe to
handle for chemical and electrochemical urination as a uorinating reagent, because they are liquid at room temperature and
involatile.

Scheme 12.

Table 9
Physical and electrochemical properties of ionic liquids (25 8C) [71].
Potential window (V vs Li+Li)c

Ionic liquid

Density (g/cm3)

Viscosity (mPa s)

Conductivity (mS/cm)

Ered (v)

Eoxi (v)

[emim][AlCl4]
[emim][H2.3F3.3]
[emim][BF4]
[emim][CF3CO2]
[emim][CH3SO2]
[emim][CF3SO2]
[emim][CF3SO2)2N]
[emim][C2F5SO2)2N]
[emim][(CF3SO2)3C]

8
9.0
11
14
39
10
15
1
39

1.29
1.14
1.24
1.29b
1.25
1.38
1.52

18
5
43
35a
160
43
28
61
181

22.6
10.00
13.0
9.6a
2.7
9.3
8.4
3.4
1.7

1.0
1.5
1.0
1.0d
1.3d
1.0
1.0
0.9
1.0

5.5
5.3
5.5
4.6d
4.9d
5.3
5.7
5.8
6.0

a
b
c
d

20 8C.
22 8C.
GC (glassy Carbon), 1 mA cm2, 20 mV s2.
pt, 50 mV, emim = 1-ethyl-3-ethyldazolium.

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

34

Scheme 13.

Table 10
Conductivity of poly (hydrogen uoride) salts [75].

Table 14
Media effect on anodic uorination of 3-phenylthiophthalide (1).

Poly (hydrogen uoride) salt

Conductivity (mS/cm)

Me4NF4HF
Et4.NF4HF
Pr00 4NF4HF
Pr00 4NF4HF
Me3N3HF

197.6
99.2
33.2
9.7
32.8

Run

Reaction media

Charge passed (F/mol)

1
2
3
4
5

Et3N3HF
Et3N4HF
Et3N5HF
Et4N4HF
Et4N5HF

4.2
4.2
3.2
3.3
4

Determined by

Yield (%)a
2

4
77
96
99
93

21

19

FNMR.

Table 11
Fluorination of phthalate (1a) under various conditions [44].
Run

Reaction
media

Supporting electrolyte

Charge
passed (F/mol)

Yield (%)

1
2
3
4
5
6
7
8

MeCN
CH2Cl2
DME

[emim][OTf]
[emim][OTf]
[emim][OTf]

Et3N5HF
Et3N5HF
Et4NF4HF
Et3N3HF
Et3N5HF
Et3N3HF
Et4NF4HF
Et3N5HF

6
8
8
4
8
6
4.7
4

16
23
0
17
16
78
70
90

Scheme 14.

Ionic liquid as uorinating agent in electrochemical uorination

process
contains N,N-dialkylimidazolium salts, showed meaning full
conductivity during electrochemical uorination of organic
compounds. The viscosity has direct relation with the alkyl group
and the conductivity of imidazolium cations, decreases with the
length of the alkyl group. The viscosity is also decreasing due to
hydrophilic interactions of ILs and drastically decreases with the
addition of smaller amount of water. It was that the ethyl and
methyl imidazolium (emim) salt showed good conductivity among
that series [75] (Scheme 13).

Table 12
Effect of supporting electrolyte on anodic mono-ourination of 1-phenyl-3(phenylthio)oxiindole [85].
Run

Supporting electrolyte

Charge passed (F/mol)

Yield (%)

1
2
3
4
5

Et3N2HF
Et3N3HF
Et4NF2HF
Et4NF3HF
Me4NF4HF

6
6
4
3.7
3.5

3
30
41
58
64

ILs used as media at room temperature in many organic

syntheses reaction [49,76,77,57,78,79,25] alkyl ammonium hydrogen uoride salts have been reported for solvent free anodic
uorination [8084]. Some researcher uses ILs in electro organic
syntheses as shown in Table 11 [57,78,79,25], Table 12 [85]
(Scheme 14).
Anodic uorination of 2-cyano1-methylpyrrole (1) using
various uoride supporting salts in MeCN. The results are
summarized in Tables 13 and 14 (Scheme 15).
Et3N2HF and Et4NF.4HF were used as supporting electrolyte to
decrease the potential needs for anodic electrochemical uorination of 1a. But the yield of the compounds in ILs Et3N2HF was very
low (run2). 1a was starting to consume after passing two (2 F/Mol)
when Et4NF.4HF was used. But no by product was formed (run 3).
Due to the above evidence, Et3N3HF was considered, suitable
for electrochemical uorination to organic compounds [86,87]
(Scheme 16).

Table 13
Anodic uorination of 2-cyano1-methylpyrrole (1) using various uoride supporting salts in MeCN [85].
Run

Supporting electrolyte (1 M)

1
2
3
4

Et3N2HF
Et3N3HF
Et35HF
Et4NF4HF

Determination by 19 FNMR spectroscopy.

Yield(%)a
2

20
5
0
0

Trace
2
12
21

32
65
5
6

Trace
3
54
28
Scheme 15.

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

35

Scheme 16.

Figs. 3 and 4 show the potential curve for oxidation of MCN

containing 1.0 M Et3N2HF and 1.0 M Et3N3HF both in the
presence and absence of 1a. From the Fig. 1, it is clear that less
potential are needed to oxidize Et3N3HF as compare with 1a. The
1a to Et3N3HF/MeCN solution cathodic shift was observed as
shown in Fig. 4 [88] (Scheme 17).
Fluorination of 3-phenylthiophthalide was carried out in
various liquid uoride salts without a solvent [89].
Fig. 3. Current densitypotential curves in MeCN (0.1 M 1a in 1.0 M Et3N2HF).

Electrochemical anodic uorination to heterocyclic containing

Sulfur compounds like 2-ethoxycarbonyl-4,4-dimethyl-3-thiolanone
has been studied, as shown in Scheme 18 [90].
Electrochemical uorination in an undivided cell in anhydrous
MCN and platinum was used as electrodes. Fluoride salts are used
as uorination sources and also as solvent. Anodic uorinations of
1a are shown in Table 15 [91].

Scheme 17. Fluorination of 2-cyano-1-methylpyrrole (1a) 16.

Fig. 4. Current densitypotential curves in MeCN (0.1 M 1a in 1.0 M Et3 N3HF).

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

36

Scheme 18.

Table 15
Fluorination of O-methyl S-benzyl thio carbonate (1a).
Run

Solvent

Supporting electrolyte (1M)

Current density (mA/cm2)

Electricity (F/mol)

Yielda (%)
3a

2a
1
2
3
4
5
6
7
8
9
10
11
12
a
b

CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
DME
DME

Determined by
Isolated yield.

19

Et4NF-4HF
Et4NF-5HF
Et4NF-4HF
Et4NF-4HF
Et4NF-4HF
Et4NF-4HF
Et4NF-4HF
Et4NF-4HF
Et4NF-4HF
Et3NF-5HF
Et4NF-4HF
Et3NF-5HF

10
10
10
10
5
5
15
15
10
10
10
10

4
4
5
7
4
6
5
6
4
4
4
4

50 (38)
17
28
9
37
25
40
28
17
20
38
22

Trace
0
3
6
0
1
4
4
0
0
0
0

F NMR.

Anodic mono uorination was studied in detail while using Nacetyl-2-oxazolidinone (2a) as reference compounds. The uorination process was carried out in undivided cell, using MCN as
solvent and variation of current. During the process Et4NF-5HF was
used as supporting as well sources of Fluoride ion sources. a-mono
uorinated 4a product was obtained through electrochemical
methods. Figs. 5 and 6 showed the relation of current passed and
percentage of products yield [92].

Quite recently successfully cyclic a-mono Fluoro phosphate

esters were prepared by using anodic uorination and ring-closing
Olen metathesis as shown in Scheme 19 [93,94].
Compounds 1,3-oxathiolanones and 1,3-dithiolanones not
suppress the passivation and negligible amount of yield. However,
if stable Et4NF4HF is used, both the current efciency and the
percentage yield increase in anhydrous MCN electrolytic solution,
as shown in Scheme 20 [9398].

Fig. 5. Relationship between the yield of 4a and electricity, Current density: 15.

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

37

Fig. 6. Relationship between the yield of 4a and current density. Electricity: 15 F/mol.

Scheme 19.

The anodic oxidation of 5a (cumene) was more positive when

compare with Toluene 1 and ethyl benzene 3, as alkyl group have a
positive inductive effect. Anodic oxidation of 1, 3, and 5a was
performed in Et4NF-4HF/MeCN system and constant current.
Anodic uorination proceeds and provided benzilic uorinated 2,
4, and 6a products aceta mediation take place simultaneously,
except for 5a [97] As shown in Scheme 21.
Conclusion
Scheme 20.

Scheme 21.

Due to commercial and pharmacological importance of

uorinated organic compounds, most of the researcher pays
attention to selective electrochemical uorination. Carbon, platinum and nickel showed promising materials to be used as an
electrode in electrochemical uorination of organic compounds.
Among these, a binary uoride of nickel was extensive evaluated
for its good electrochemical properties. The electrolytes like
Et3NFnHF and Et3NFnHF were noticed as a good uorinating
agent during electrochemical uorination in the presence of
CH3CN solvent. In per uorination process the anhydrous HF (AHF)
was commonly used. Different type of solvents such CH3CN, DMC,

38

Z.U.H. Khan et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 2638

DME, THF etc. is generally used for electro uorination to organic

compounds, but each solvent shows some effect, during electrochemical uorination and also affected the products formed during
the process. Ionic Liquid (IL) due to its green nature and having a
wide electrochemical window was evaluated for electrochemical
uorination to an organic compound. Different types of ILs such as
(Et3N3HF, Et4NF3HF, Py-NHF, HF, Me4NF4HF, Et4NF4HF,
Pr00 4NF4HF, Bu00 4NF4HF, and Me3N3HF) are used for electrochemical uorination to organic compounds. The preparation and
use of ionic liquid HF salts in electrochemical uorination has
overcome the problems of low boiling point and hard corrosivity
associated with the use of HF because of liquid state and less
corrosive nature of ionic liquids. The use of ionic liquids in general
was observed to increase the yield and efciency of the
uorination process. Our research group got some good result
used IL Et3N3HF as a uorinating agent for selected organic
compounds.

[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]

Acknowledgment
The authors are thankful to China Scholarship Council (No.
2012GXZ174) and the Fundamental Research Funds for the Central
Universities (YS1406) for support of this research work.
References
[1] R. Filler, Y. Kobayashi (Eds.), Biomedicinal Aspects of Fluorine Chemistry, Kodansha & Elsevier Biomedical, Tokyo, 1982.
[2] J.T. Welch, Tetrahedron 43 (1987) 3123.
[3] J.T. Welch, S. Eswarakrishnan, Fluorine in Bioorganic Chemistry, Wiley, New York,
1991.
[4] H. Yoshioka, C. Nakayama, N.J. Matsuo, Synth. Org. Chem. Jpn. 42 (1984) 809.
[5] M. Johno, K. Itoh, J. Lee, Y. Ouchi, H. Takezoe, A. Fukuda, T. Kitazume, Jpn. J. Appl.
Phys. 29 (1990) L107.
[6] N. Rozhkov, Russ. Chem. Rev. 45 (1976) 615.
[7] I.N. Rozhkov, M.M. Baizer, H. Lund (Eds.), Organic Electrochemistry, 2nd ed.,
Marcel Dekker, New York, 1983 (Chapter 24).
[8] E. Holitzer, P. Sartori, Chem. Ing. Tech. 58 (1986) 19.
[9] P. Sartori, Bull. Electrochem. 6 (4) (1990) 471.
[10] W.V. Childs, L. Chtistensen, F.W. Klink, C.F. Koplin, in: M.M. Baizer, H. Lund (Eds.),
Organic Electrochemistry, 3rd ed., Marcel Dekker, New York, 1991 (Chapter 24).
[11] D. Landini, A. Maia, A. Rampoldi, J. Org. Chem. 54 (1989) 328.
[12] T. Fuchigami, S. Higashiya, S. Hou, K. Dawood, Rev. Heteroat. Chem. 19 (1999) 67.
[13] T. Fuchigami, in: P.S. Mariano (Ed.), Advances in Electron-Transfer Chemistry, vol.
67, JAI Press, Greenwich, CT, 1999, p. 4.
[14] T. Fuchigami, in: O. Hammerich, H. Lund (Eds.), Organic Electrochemistry, 4th ed.,
Dekker, New York, 2001, p. 1035.
[15] S. Torii:, in: H.F. Ebel (Ed.), Electro Organic Synthesis Methods and Applications;
Part I: Oxidations; Monographs in Modern Chemistry, Kodansha, Tokyo, 1985.
[16] J.H. Simons, Trans. Electrochem. Soc. 95 (1949) 47.
[17] D. Nenitzescu, Rev. Roum. Chim. 52 (5) (2007) 453.
[18] N. Muhammad, Z. Man, M.A. Bustam, M.I.A. Mutalib, S. Raq, J. Ind. Eng. Chem. 19
(1) (2014) 207.
[19] Anguo Ying, Zhifeng Li, Yuxiang Ni, Songlin Xu, Hailiang Hou, Huanan Hu, J. Ind.
Eng. Chem. 24 (2015) 127.
[20] L. Duchet, J.C. Legeay, D. Carrie, L. Paquin, J.J. Vanden Eynde, J.P. Bazureau,
Tetrahedron 66 (2010) 986.
[21] K. Raj Singh, P. Gupta, O.P. Sharma, S.S. Raya, Ind. Eng. Chem. 24 (2015) 14.
[22] M.V.B. Zanoni, E.I. Rogers, C. Hardacre, R.G. Compton, Anal. Chim. Acta 659 (2010)
115.
[23] Y. Wei, C. Keke, Z. Xiaofang, K. Yingying, T. Xiujuan, H. Xiaoxiang, Ind. Eng. Chem.
(2015), http://dx.doi.org/10.1016/j.jiec.2015.04.002.
[24] N. Fontanals, S. Ronka, F. Borrull, A.W. Trochimczuk, R.M. Marce, Talanta 80
(2009) 250.
[25] K.R. Seddon, J. Chem. Technol. Biotechnol. 68 (1997) 351.
[26] P. Sartori, N. Ignatev, J. Fluor. Chem. 87 (1998) 157.
[27] Y.W. Alsmeyer, W.V. Childs, R.M. Flynn, G.G.1. Moor, J.C. Smeltzer, in: R.E. Banks, B.E.
Smart, J.C. Tatlow (Eds.), Organouorine Chemistry, Plenum, p. 121 (Chapter 5).
[28] T. Gramstad, R.N. Haszeldine, J. Chem. Soc. (1956) 173.
[29] P. Kubisa, Prog. Polym. Sci. 34 (2009) 1333.
[30] E. Laurent, B. Marquet, R. Tardivel, Tetrahedron 45 (1989) 4431.
[31] J.H. Meurs, W. Eilenberg, Tetrahedron 47 (1991) 705.
[32] A.G. Doughty, M. Fleischmann, D. Pletcher, J. Electroanal. Chem. 51 (1974) 329.
[33] J.H. Simons, Fluorine Chemistry, vol. 1, Academic Press, New York, 1950p. 414.
[34] T. Gramstead, R.N. Haszeldine, J. Chem. Soc. (1956) 173.
[35] Peter Sartori, J. Fluor. Chem. 103 (2000) 57.

[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]

[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
[96]
[97]
[98]

J. Burden, J.C. Tatlow, Adv. Fluor. Chem. 1 (1960) 129.

M. Page, C. R. Acad. Sci. 246C (1967) 2094.
L. Stein, J.M. Neil, G.R. Alms, Inorg. Chem. 11 (1969) 2472.
V.Ya. Semenii, V.V.A. Stepanov, N.V. Ignatev, G.G. Furin, L.M. Yagupolskii, Zh.
Obshch. Khim. 55 (1985) 2716.
E. Laurent, B. Marquet, R. Tardivel, J. Fluor. Chem. 49 (1990) 115.
A. Bensadat, G. Bodennec, E. Laurent, R. Tardivel, J. Fluor. Chem. 20 (1982) 333.
H. Benotmane, A. Bensadat, J. Sot. Alger. Chim. 73 (1991) 1.
Toshio Fuchigami, Akinori Konno, Kiyono Nakagawa, Moriyasu Shimojo, J. Org.
Chem. 59 (1994) 5937.
Y. Hou, T. Fuchigami, J. Electrochem. Soc. 1 (47) (2000) 4567.
M.R. Shaaban, H. Ishii, T. Fuchigami, J. Org. Chem. 65 (2000) 8685.
F. Huba, E.B. Yeager, G.A. Olah, Electrochim. Acta 24 (1979) 489.
E.V. Nikitin, Y.A. 1gnatev, A.S. Romakhim, O.V. Parakin, G.V. Romanov, Y.M. Kargin,
A.N. Pudovik, Zh. Obshch. Khim. 52 (1982), 1024-1.
Masaru Hasegawa, Hideki Ishii, Toshio Fuchigami, Green Chem. 5 (2003) 512.
T. Fuchigami, M. Shimojo, A. Konno, K. Nakagawa, J. Org. Chem. 55 (1990) 6074.
V. Suryanarayanan, S. Chellammal, M. Noel, J. Fluor. Chem. 93 (1999) 53.
T. Brigaud, E. Laurent, Tetrahedron Lett. 31 (1990) 2287.
T. Fuchigami, A. Konno, M. Shimojo, J. Org. Chem. 60 (1995) 3459.
T. Fuchigami, T. Sunaga, H. Ishii, M. Atobe, in: Proceedings of the100th ECS
Meeting, Philadelphia, May, 2002 (abstract 1220).
T. Konno, J. Fuchigami, Appl. Electrochem. 25 (1995) 690.
K. Suda, K. Hotoda, M. Aoyagi, T. Takanmi, J. Chem. Soc. Perkin Trans. 11 (1995)
1327.
T. Fuchigami, A. Konno, K. Nakagawa, M. Shimoja, J. Org. Chem. 59 (1994) 5937.
S. Narizuka, T. Fuchigami, J. Org. Chem. 58 (1993) 4200.
S. Narizuka, H. Koshiyama, A. Konno, T. Fuchigami, J. Fluor. Chem. 73 (1995) 121.
A. Konno, T. Fuchigami, J. Appl. Electrochem. 25 (1995) 173.
P. Sartori, N. Ignatev, S. Datsenko, J. Fluor. Chem. 75 (1995) 157.
D.W. Yin, D.S. Zarkowsky, D.W. Thomas, M.M. Zhao, M.A. Huffman, Org. Lett. 6 (9)
(2004) 1465.
I.N. Rozhkov, Russ. Chem. Rev. 45 (1976) 615.
W.V. Childs, L. Christensen, F.W. Mink, C.F. Kolpin, in: H. Lund, M.M. Baizer (Eds.),
In Organic Electrochemistry, 3rd ed., Marcel Dekker, New York, 1991 (Chapter
26).
I.L. Knunyants, I.N. Rozhkov, A.V. Bukhtiarov, M.M. Goldin, R.V. Kudryawtseu, Izv.
Akad. Nauk. SSR Ser. Khim. 1207 (1970).
I.N. Rozhkov, A.V. Bukhtiarov, N.D. Kuleshova, I.L. Knunyants, Dokl. Akad.
Nauk. SSSR 193 (1970) 1322.
T. Fuchigami, Rev. Heteroat. Chem. 10 (1994) 155.
T. Fuchigami, M. Sano, J. Electroanal. Chem. 414 (1996) 81.
H. Schmidt, H.D. Schmidt, Chem. Tech. (Berlin) 5 (1953) 454.
H. Schmidt, H.D. Schmidt, J. Pract. Chem. 2 (1955) 105.
H. Schmidt, H. Meinert, Angew. Chem. 72 (1960) 109.
I.L. Knunyants, I.N. Rozhkov, A.V. Bukhtiarov, M.M. Goldin, R.V. Kudryavvtseu, Izv.
Akad. Nauk. SSSR. Ser. Khim. 73 (1970) 65.
I.N. Rozhkov, A.V. Bukhtiarov, N.D. Kuleshova, I.L. Knunyants, Dokl. Akad. Nauk.
SSSR 193 (1970) 1322, CA. 74 (1971) 70-878.
I.L. Knunyants, I.N. Rozhkov, A.V. Bukhtiarov, Izv. Akad. Nauk. SSSR. Ser. Chem.
478 (1971) 1369.
E.V. Nikitin, Y.A. 1gnatev, A.S. Romakhim, O.V. Parakin, G.V. Romanov, Y.M. Kargin,
A.N. Pudovik, Zh. Obshch. Khim. 52 (1982) 1207.
G. Alvemhe, A. Laurent, E. Laurent, R. Tardivel, Ann. Chim. Fr. (Paris) 9 (1984) 659.
T. Fuchigami, S. Narizuka, A. Konno, J. Org. Chem. 57 (1992) 3755.
A. Konno, W. Naito, T. Fuchigami, Tetrahedron Lett. 33 (1992) 7017.
S. Narizuka, A. Konno, H. Matsuyama, T. Fuchigami, Denki Kagaku 61 (1993) 868.
J.L. Anderson, J. Ding, T. Welton, D.W. Armstrong, J. Am. Chem. Soc. 124 (2002)
142.
T. Welton, Chem. Rev. 99 (1999) 2071.
J.D. Holbrey, K.R. Seddon, Clean Prod. Process. 1 (1999) 223.
H. Ishii, T. Fuchigami, Electrochemistry 70 (2002) 46.
P. Wasserscheid, W. Keim, Angew. Chem. Int. Ed. 39 (21) (2000) 3772.
R. Sheldon, Chem. Commun. (2001) 2399.
M. Hasegawa, H. Ishii, T. Fuchigami, Tetrahedron Lett. 43 (2002) 1503.
K. Momota, M. Morita, Y. Matsuda, Electrochim. Acta 38 (1993) 1123.
S. Chen, T. Hatakeyama, T. Fukuhara, S. Hara, N. Yoneda, Electrochim. Acta 42
(1997) 1951.
Yankun Hou, Seiichiro Higashiya, Toshio Fuchigami, J. Org. Chem. 62 (1997) 8773.
G. Cerichelli, M.E. Crestoni, S. Fornarini, Gazz. Chim. Ital. 120 (1990) 749.
A.W. Erian, A. Konno, T. Fuchigami, J. Org. Chem. 60 (1996) 7654.
Toshiki Tajima, Hideki Ishii, Toshio Fuchigami, Electrochem. Commun. 3 (8)
(2001) 467.
Masaru Hasegawa, Toshio Fuchigami, Electrochim. Acta 49 (2004) 3367.
Yi Cao, Toshio Fuchigami, Electrochim. Acta 51 (2006) 2477.
Yi Cao, Toshio Fuchigami, J. Electroanal. Chem. 587 (2006) 25.
Yi Cao, Katsutoshi Suzuki, Toshiki Tajima, Toshio Fuchigami, Tetrahedron 61
(2005) 6854.
Bakenova Zagipa, Asami Hidaka, Yi Cao, Toshio Fuchigami, J. Fluor. Chem. 127
(2006) 552.
Toshio Fuchigami, J. Fluor. Chem. 128 (2007) 311.
Toshiki Tajima, Hideki Ishii, Toshio Fuchigami, Electrochem. Commun. 4 (2002)
589.