Indium-mediated radical addition of perfluoroalkyl iodide in water

Article abstract of DOI:10.1016/j.jfluchem.2011.03.001

Reaction of perfluoroalkyl groups with carbon-carbon unsaturated compounds using indium in water proceeded smoothly to provide the addition products in high yields.

Full text of DOI:10.1016/j.jfluchem.2011.03.001

Journal of Fluorine Chemistry 132 (2011) 427–429
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Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Short communication
Indium-mediated radical addition of perfluoroalkyl iodide in water
Toshiyuki Takagi *, Toshiyuki Kanamori
Research Center of Stem Cell Engineering (RCSC), National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-
8
565, Japan
A R T I C L E I N F O
A B S T R A C T
Article history:
Reaction of perfluoroalkyl groups with carbon–carbon unsaturated compounds using indium in water
proceeded smoothly to provide the addition products in high yields.
ß 2011 Elsevier B.V. All rights reserved.
Received 9 December 2010
Received in revised form 7 March 2011
Accepted 7 March 2011
Available online 1 April 2011
Keywords:
Indium
Perfluoroalkyl iodide
Water
Radical addition
Carbon–carbon unsaturated compound
1
. Introduction
Many fluorinated compounds exhibit unique properties such as
Vallejo and Postigo reported the intermolecular radical perfluor-
oalkylation reaction in water [18]. This reaction required 1,1 -
0
azobis(cyclohexanecarbonitrile) or dioxygen as the radical initia-
tor, and tris(trimethylsilyl)silane as the reducing agent.
In this paper, we report the introduction of perfluoroalkyl
groups into carbon–carbon unsaturated compounds using indium
metal in water without employing organic solvents. This reaction
proceeds under mild conditions and provides the addition
products with high yields.
thermal and chemical stability, and noteworthy hydrophobicity
and lipophilicity, and new methods for their synthesis are being
widely investigated [1–6]. We have already reported the synthesis
of fluorinated fatty acids or double chained phosphatidylcholines
and their interfacial properties [7–11]. Surface pressure-area
isotherms of their monolayers at the air/water interface were
measured to consider the effect of fluorine substituents on their
interfacial stability, and as a result, the introduction of fluorine
atoms was found to improve the interfacial stability of monolayers.
Many studies on synthesis with perfluoroalkyl iodides using
several metals as initiators for the radical reactions have already
been carried out [12,13]. The intermolecular carbon–carbon bond
formation reactions are initiated by copper [14], iron [15], Raney
nickel [16], etc. and are achieved in organic solvents or organic–
water mixture solvents. While intermolecular radical perfluor-
oalkylation reactions in water have attracted attention in the field
of fluorine chemistry, reports of the addition reaction in water are
rare. Blancou and co-workers reported that the reaction of
perfluoroalkyl iodide with 2-methyl-3-butyn-2-ol produced an
addition product in the presence of zinc in water [17]. However,
severe conditions (110 8C, 17 h) are needed to obtain the
compound, and their approach has not been widely employed
for reductively initiated addition reactions in water. Recently,
2. Results and discussion
Indium has been demonstrated to be an efficient and promising
metal for mediating organic reactions in aqueous media [19–23].
Indium-mediated carbon–carbon bond-forming reactions in aque-
ous media have been of great importance both economically and
environmentally. Recently, Naito and co-workers reported the
addition of an indium-mediated alkyl radical to an electron-
deficient C 55 N bond or C 55 C bond [23]. However, the addition of an
indium-mediated perfluoroalkyl radical to C 55 C bonds has yet to be
studied. Thus, our goal was to develop the reaction of perfluor-
oalkyl iodides with carbon–carbon unsaturated compounds in
aqueous media in the presence of indium.
We found that when indium powder was added to
heterogeneous aqueous mixture of perfluorobutyl iodide (1) and
-decen-1-ol (2), the addition product 3 was obtained. Thus, we
a
9
studied a way to optimize the reaction conditions as shown in
Table 1. An examination of the mole ratio perfluorobutyl iodide
(1):9-decen-1-ol (2):indium at room temperature revealed the
highest yield of 3 when the 2:1:In ratio was 1:2:0.5 (run 4 in Table
*
Corresponding author. Tel.: +81 29 861 6392; fax: +81 29 861 4651.
E-mail address: t.takagi@aist.go.jp (T. Takagi).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.03.001

4
28
T. Takagi, T. Kanamori / Journal of Fluorine Chemistry 132 (2011) 427–429
Table 1
Reaction of perfluorobutyl iodide (1) with 9-decen-1-ol (2) in the presence of indium
Run
Molar ratio 2:1:In
Product 3 (%)
Recovery 2 (%)
a
a
1
2
3
4
5
1:1:1
33
18
1:2:1
54
57
78
–
–
–
1:3:1
1:2:0.5
1:2:0.2
a
a
29
64
a
1
Yields were estimated by H NMR.
Scheme 1. Reaction of perfluorobutyl iodide (1) with carbon–carbon unsaturated compounds in the presence of indium.
Scheme 2. Reaction of 9-decen-1-ol (2) with alkyl halides (8, 10–12) under indium in water.
1
). In the course of the purification of this reaction, the compound 3
oalkyl reagent with iodine to produce the addition product in
water.
can be easily separated with column chromatography.
As an extension of this reaction, we chose 3-butyn-1-ol (4) as a
compound containing a carbon–carbon triple bond and allylben-
zene (6) as an aromatic compound. The reaction of 4 was examined
using the same reaction conditions as those used for 2 and gave the
corresponding product 5 [24] in a similar way. The E/Z ratio of 5
In conclusion, we succeeded in introducing perfluoroalkyl
moieties into carbon–carbon unsaturated compounds using
indium in water. Our method provides a new route using indium
metal for the synthesis of fluorinated compounds in water.
1
was estimated to be 1/0.14 based on H NMR. Next, the reaction of
3. Experimental
6
was carried out at room temperature using a similar molar ratio,
but the starting material 6 was recovered. Thus, the temperature
was raised to 50 8C to provide the corresponding product 7 [25] in a
high yield (Scheme 1).
3.1. Instruments
1
19
H and F NMR spectra were measured on a JEOL JNM-LA 600
FT-NMR system (600 MHz) using TMS and CFCl as internal
Further, we examined the reaction of perfluorooctyl iodide (8),
perfluorooctyl bromide (10), 1-iodo-1H,1H,2H,2H-nonafluorohex-
ane (11) and 1-iodobutane (12) with 9-decen-1-ol (2). Although
the reaction of 2 with 8 as the perfluorobutyl iodide in the presence
of indium in water proceeded as shown in Scheme 2 and produced
the corresponding addition product 9 [8] in a high yield, the
starting material 2 was recovered for the reagents bearing
hydrogen atoms as 11 and 12, or the perfluoroalkyl reagent
bearing bromine instead of iodine as 10. Thus, we found that the
indium-mediated reaction proceeded smoothly using a perfluor-
3
standards, respectively. Mass spectra (ESI–MS) were measured on
a JEOL JMS-700T Tandem MStation. Column chromatography
purifications were carried out using silica gel 60 (Merck 7734).
3.2. Materials
Perfluorobutyl iodide, perfluorooctyl iodide and 1-iodo-
1H,1H,2H,2H-nonafluorohexane were purchased from Daikin
Finechemical Laboratory (Japan). Perfluorooctyl bromide and 1-

T. Takagi, T. Kanamori / Journal of Fluorine Chemistry 132 (2011) 427–429
429
iodobutane were purchased from Tokyo Chemical Industry Co., Ltd.
Japan). Indium powder was purchased from Lancaster and its
purity was over 99%.
dm, J = 268.41 Hz), ꢀ114.47 (1F, dm, J = 268.41 Hz), ꢀ125.03 (2F,
m), ꢀ126.38 (2F, m).
(
3.2.4. 11,11,12,12,13,13,14,14,15,15,16,16,17,17,18,18,18-
3.2.1. 11,11,12,12,13,13,14,14,14-Nonafluoro-9-iodotetradecan-1-ol
Heptadecafluoro-9-iodooctadecan-1-ol (9)
(
3)
To a heterogeneous mixture of 9-decen-1-ol (2, 157 mg,
1.0 mmol) and perfluorooctyl iodide (8, 1.095 g, 2.0 mmol) in
water (1 ml) was added indium powder (57 mg, 0.5 mmol), and
this mixture was stirred at 50 8C for 18 h. The aqueous mixture was
To a heterogeneous mixture of 9-decen-1-ol (2, 155 mg,
.0 mmol) and perfluorobutyl iodide (1, 708 mg, 2.0 mmol) in
1
water (1 ml) was added indium powder (57 mg, 0.5 mmol), and
this mixture was stirred at room temperature for 18 h. The
aqueous mixture was subjected to direct column chromatography
2
subjected to direct column chromatography on SiO (ca. 80 g) with
hexane/EtOAc (7/3) as an eluent to give 9 (573 mg, 81%) [8]. NMR
shifts of 9 were congruent with the shifts of the compound in ref.
on SiO
387 mg, 78%).
: Colorless liquid. ESI–MS m/z: 503 (M+H) . HRMS (ESI) calcd.
2
(ca. 80 g) with hexane/EtOAc (7/3) as an eluent to give 3
(
[8].
+
1
3
9: Colorless waxy solid. H NMR (CDCl
3
)
d
: 1.26–1.46 (10H, m),
+
1
for C14
CDCl
m), 2.72–2.82 (1H, m), 2.87–2.97 (1H, m), 3.64 (2H, t, J = 6.59 Hz),
H
21OF
9
I (M+H) 503.0493; Found: 503.0499. H NMR
1.50–1.61 (3H, m), 1.80 (2H, m), 2.78 (1H, m), 2.92 (1H, m), 3.64
1
9
(
3
)
d
: 1.37–1.46 (10H, m), 1.50–1.60 (3H, m), 1.73–1.83 (2H,
3
(2H, td, J = 6.59 Hz), 4.33 (1H, tt, J = 8.61, 4.33 Hz). F NMR (CDCl )
ppm: ꢀ81.29 (3F, t, J = 9.19 Hz), ꢀ112.23 (1F, dm, J = 272.08 Hz),
ꢀ115.07 (1F, dm, J = 272.08 Hz), ꢀ122.03 (2F, bs), ꢀ122.38 (4F, bs),
ꢀ123.19 (2F, bs), ꢀ124.07 (2F, bs), ꢀ126.60 (2F, m).
19
4
.33 (1H, m). F NMR (CDCl
3
) ppm: ꢀ81.55 (3F, t, J = 9.19 Hz),
112.48 (1F, dm, J = 268.41 Hz), ꢀ115.33 (1F, dm, J = 268.41 Hz),
125.06 (2F, m), ꢀ126.39 (2F, m).
ꢀ
ꢀ
Acknowledgement
3
.2.2. 5,5,6,6,7,7,8,8,8-Nonafluoro-3-iodo-3-octen-1-ol (5)
To heterogeneous mixture of 3-buyn-1-ol (4, 74 mg,
.1 mmol) and perfluorobutyl iodide (1, 726 mg, 2.1 mmol) in
a
We thank Drs. Masanori Tamura and Masao Shimizu of AIST for
fruitful discussions.
1
water (1 ml) was added indium powder (58 mg, 0.5 mmol), and
this mixture was stirred at room temperature for 18 h. The
aqueous mixture was subjected to direct column chromatography
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C
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10
F
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