Radical addition of perfluoroalkyl iodides to alkenes and alkynes initiated by sodium dithionite in an aqueous solution in the presence of a novel fluorosurfactant

Article abstract of DOI:10.1002/cjoc.201300433

A new fluorinated anionic surfactant Cl(CF₂) ₆O(CF₂)₂SO₃N(C₂H ₅)₄ was prepared and characterized. The application of the fluorosurfactant allowed the fluoroalkylation to occur in the water without adding organic solvent. The addition of perfluoroalkyl iodides with olefins and alkynes under the initiation of Na₂S₂O₄ in water in the presence of the fluorosurfactant gave the corresponding adducts in good to excellent yields. The fluorosurfactant was suitable for a radical addition process. A new surfactant Cl(CF₂)₆O(CF ₂)₂SO₃N(C₂H₅) ₄ was prepared and its properties were measured. The fluorinated surfactant was applied to the fluoroalkylation of perfluoroalkyl iodides with olefins and alkynes. The reactions gave the corresponding adducts in water and avoided the use of organic solvent. The aqueous solution with the surfactant proved to be an effective medium for a radical process. Copyright

Full text of DOI:10.1002/cjoc.201300433

FULL PAPER
DOI: 10.1002/cjoc.201300433
Radical Addition of Perfluoroalkyl Iodides to Alkenes and
Alkynes Initiated by Sodium Dithionite in an Aqueous
Solution in the Presence of a Novel Fluorosurfactant
Zhiwei Xiao, Huawei Hu, Jiaoli Ma, Qingyun Chen,* and Yong Guo*
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China
A new fluorinated anionic surfactant Cl(CF2)6O(CF2)2SO3N(C2H5)4 was prepared and characterized. The appli-
cation of the fluorosurfactant allowed the fluoroalkylation to occur in the water without adding organic solvent. The
addition of perfluoroalkyl iodides with olefins and alkynes under the initiation of Na2S2O4 in water in the presence
of the fluorosurfactant gave the corresponding adducts in good to excellent yields. The fluorosurfactant was suitable
for a radical addition process.
Keywords surfactant, fluorine, aqueous, sodium dithionite, radical
Introduction
Surfactants may act as wetting agents, detergents,
foaming agents, emulsifiers, and dispersants. Among
them, fluorinated surfactants have found much more
interest since very low critical micellar concentration
values have been assessed. They are usually composed
of a hydrophilic group and a perfluorinated chain which
make them more efficient than hydrogenated ones since
their surface tensions are lower.[27-29] Perfluorooctane
sulfonate (PFOS) is a fully fluorinated anion, which is
commonly used as a simple salt (such as potassium,
sodium, or ammonium) or incorporated into larger
polymers. Because of the excellent surface activity
function, it was widely used in electronic, electroplating,
agricultural medicine, fire fighting, oil industries and
paper coatings such as fast-food wrappers. However,
PFOS is persistent in the environment and can be bio-
magnified through the food chain.[30-32] It was added to
Annex B of the Stockholm Convention on Persistent
Organic Pollutants in May 2009.[33] During the past
years, great efforts have been done to find the project to
examine the possibilities of replacing the use of PFOS.
For example, a positive result has been done by trying
to shorten the chain or add other atoms on the original
structure of PFOS by Dupont and 3M.[30,34] A lot of re-
searches have also been done in China, a famous repre-
sentative would be X(CF2)6O(CF2)2SO3K (F53, X＝
F/Cl) which has the similar structure of PFOS and has
been successfully used as chrome-fog depressant.[35,36]
Because of the urgency of the alternatives, on the
other hand, F53 has the similar or superior properties in
some aspects compared to PFOS and it may be biode-
Due to the unique nature of fluorine, the introduction
of fluorine into an organic molecule can profoundly
change the properties of the molecule in many aspects,
including lipophilicity, bioavailability, and metabolic
stability.[1-10] Partially fluorinated organic compounds,
especially those bearing perfluoroalkyl groups are
widely used in the synthesis of novel materials, in the
design of medicinal and agricultural products and in
different branches of technology.[11]
Since the sulfinatodehalogenation reaction and the
fluoroalkylations via sulfinatodehalogenation initiation
systems were discovered by a chance observation by
Huang and his co-workers in 1981,[12-17] the reactions
have become one of the most important methodologies
to incorporate per- and polyfluoroalkyl halides into or-
ganic molecules.[18-21] In general, most of the reactions
are performed in aqueous acetonitrile solution in the
presence of Na2S2O4 and NaHCO3 at room temperature.
Because of the solubility of the reactants, H2O and ace-
tonitrile are both essential in this condition. On the other
side, the need for the use of eco-friendly or alternative
reaction media in order to accomplish organic synthetic
transformations has encouraged chemists to explore a
variety of systems, such as aqueous systems or even
water alone.[22-25]
A surfactant is an amphiphilic molecule bearing both
hydrophobic and hydrophilic parts.[26] They can lower
the surface tension of a liquid, the interfacial tension
between two liquids, or that between a liquid and a solid.
*
E-mail: yguo@sioc.ac.cn; Tel.: 0086-021-54925462; Fax: 0086-021-64166128
Received May 29, 2013; accepted July 11, 2013; published online July 19, 2013.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201300433 or from the author.
Chin. J. Chem. 2013, 31, 939—944
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939

Xiao et al.
FULL PAPER
gradable owing to the oxygen atom; it would be a good
substitute. So we started to investigate the new applica-
tion of it and its ammonium salts. In order to determine
the feasibility of its use in free radical reaction, fluoro-
alkylation via sulfinatodehalogenation initiation system
was studied here.
70
60
50
40
30
20
S3
S2
S1
.
γ
Results and Discussion
At the beginning, two of F53 derivatives such as
Cl(CF2)6O(CF2)2SO3N(C2H5)4 (S1) and Cl(CF2)6O-
(CF2)2SO3K (S2) were synthesized from Cl(CF2)6O-
(CF2)2SO2F.[37] We also synthesized CF3(CF2)5(CH2)2-
SO3Na (S3) form CF3(CF2)5(CH2)2I.[38-40] Then we in-
vestigated the surface tension (γ) of the three different
surfactants by hanging plate method using a Platinum
Lridum plate (length: 10 mm, width: 19.9 mm, thick-
ness: 0.2 mm). The results were summarized in Figure 1.
We found that the surface tensions of all the three sur-
factants were declining with the increase of their con-
centration in the beginning, and the surface tension
numbers of S1 and S2 remained constant while their
concentration decreased to 1.2 and 1.6 mmol•L−1 re-
spectively. Overall, S1 displayed the best result. Its sur-
face tension is able to reach about 21 mN•m−1.
0.0
0.5
1.0
1.5
2.0
2.5
-1
.
c/(mmol L )
Figure 1 The surface tensions of S1, S2 and S3 in various con-
centrations.
Table 1 Optimization of reaction conditionsa
150 mol% NaHCO3
150 mol% Na2S2O4
surfactant
n-C H
CF3(CF2)3CH2CHIC6H13-n
CF (CF ) CF I
+
6
13
3
2 2
2
H2O, r.t.
1a
3a
2a
Entry
Surfactant
t/h
Yieldb/%
Next, addition reaction between perfluorobutyl io-
dide (1a) and 1-octene (2a) in the presence of Na2S2O4,
NaHCO3 and different fluorinated surfactants was tested
and the results were shown in Table 1. We found that S1
was the most efficient surfactant (90% yield, Table 1,
Entry 1) compared to S2 (37% yield, Table 1, Entry 2)
and S3 (63% yield, Table 1, Entry 3). S1 and S3 dis-
played better results compared to S2. The concentration
of S2 is only able to reach about 1.8 mmol•L−1 in water
because of low solubility. So actually there was only
about 10 mg of S2 in the system while S1 was able to
dissolve fully in water. The reaction was also carried out
under the traditional sulfinatodehalogenation initiation
conditions by using H2O and MeCN as co-solvent (Ta-
ble 1, Entry 7). The yields of the two reactions are
comparable (Table 1, Entry 1 vs. Entry 7). The results
mean that the use of organic solvent can be replaced by
using catalytic amount of surfactant S1.
Then we investigated different perfluoroalkyl io-
dides 1a－1d reacted with different alkenes 2a－2h in
water in the presence of sodium dithionite, sodium bi-
carbonate and fluorinated surfactant S1 at room tem-
perature for 12 h to give the corresponding adducts 3.
As summarized in Table 2, we found that all of the per-
fluoroalkyl iodides reacted smoothly with unactivated
alkenes to give the corresponding products in good to
excellent yields in the water system. Those alkenes with
a longer chain showed better results (Table 2, Entries 1
and 4) possibly due to their higher boiling points. Func-
tional groups such as 4-toluenesulfonyl (OTs, 2e) and
hydroxyl group (2f) were tolerated under the optimized
conditions although they gave moderate yields of prod-
ucts (Table 1, Entries 5 and 7). Perfluoroalkyl iodide
1
2
S1 (60 mg)
S2 (60 mg)
S3 (60 mg)
S1 (60 mg)
S1 (40 mg)
S1 (20 mg)
－
12
12
12
24
12
12
12
90
37
63
91
86
82
88
3
4
5
6
7c
a
Unless otherwise noted, reactions were performed with 4.5
mmol of 1a, 3 mmol of 2a, and surfactant in 9.0 mL H2O. b Yield
based on 19F NMR. The reaction was carried out under tradi-
c
tional conditions: H2O (6 mL) and MeCN (3 mL) as a cosolvent.
1d which bears a SO2F group also reacted smoothly
with these unactivated alkenes (Table 1, Entries 10 to
12).
Under the same conditions, in the next we investi-
gated the fluoroalkylation reaction of perfluorobutyl
iodide (1a) with terminal alkyne 4a, but only trace
product was detected in this case (Table 3, Entry 1).
Increasing the temperature to 50 ℃ afforded the de-
sired E/Z mixture of (3,3,4,4,5,5,6,6,6-nonafluoro-1-
iodohex-1-en-1-yl)benzene (5aa) in 71% yield (Table 3,
Entry 2). Other terminal alkynes such as 1-octyne,
4-fluorophenylacetylene and 2-ethynylpypridine were
also able to react with perfluoroalkyl iodides to give the
corresponding adducts in good yields in this water sys-
tem (see Table 3). A lot of aromatic and heteroaromatic
compounds such as 1,4-dimethoxybenzene, indole,
N-methylindole and aminothiazole were also investi-
gated. However, they afforded very low yields probably
due to their low reactivities and solubilities.
940
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Chin. J. Chem. 2013, 31, 939—944

Radical Addition of Perfluoroalkyl Iodides to Alkenes and Alkynes Initiated by Sodium Dithionite
Table 2 The reactions of perfluoroalkyl iodides with olefins in
reaction without organic solvent. This method provides
a practical method for the preparation of useful products
bearing perfluoroalkyl groups in water system.
watera
Na2S2O4/NaHCO3/surfactant
+
RFI
R1CH CH2
RFCH2CHIR1
H2O, r.t., 12 h
1
2
3
Experimental
RF = n-C4F9 (a), n-C6F13 (b), ClCF2CF2CF2CF2 (c),
FSO2(CF2)2O(CF2)4 (d). R1 = n-C6H13 (a), n-C4H9 (b),
t-Bu (c), Cyclohexyl (d), CH2CH2OTs (e), CH2CH2OH (f),
n-C3H7 (g), CH2CH(CH3)2 (h)
General information for the sulfinatodehalogenation
reaction
All reagents were used as received from commercial
sources, unless specified otherwise, or prepared as de-
scribed in the literature. 1H NMR spectra were recorded
on a Bruker AM 400 (400 MHz) spectrometer with
TMS as an internal standard (negative for upfield). 19F
NMR spectra were recorded on a Bruker AM 400 (376
MHz) with CFCl3 as an external standard (negative for
upfield). 13C NMR spectra were recorded on a Bruker
AV-400 (100 MHz) spectrometer with CDCl3 as an in-
ternal standard (negative for upfield). MS and HRMS
were recorded on a Hewlett–Packard HP-5989A spec-
trometer and a Finnigan MAT-8483 mass spectrometer.
Infrared spectra were measured with a Perkin-Elmer
983 spectrometer. Column chromatography was per-
formed using silica gel (mesh 300－400). All solvents
were purified by standard methods.
Entry
RFI
Olefin
Product
Yieldb/%
1
2
1a
1a
1a
1a
1a
1b
1b
1c
1c
1d
1d
1d
2a
2b
2c
2d
2e
2b
2f
3aa
3ab
3ac
3ad
3ae
3bb
3bf
3ca
3cd
3da
3dg
3dh
90
63
77
90
53
81
69
77
75
71
61
61
3
4
5
6
7
8
2a
2d
2a
2g
2h
9
10
11
12
Synthesis of Cl(CF2)6O(CF2)2SO3N(C2H5)4 (S1): To
a solution of Cl(CF2)6O(CF2)2SO2F (5.38 g, 10 mmol)
in chlorobenzene (25 mL) was added Et3N (1.01 g, 10
mmol) and (C2H5O)3SiCH3 (1.46 g, 10 mmol). The mix-
ture was stirred at r.t. for 9 h. During this time, a great
quantity of white solid precipitated from the system.
The residue was filtered and then recrystallized in
chlorobenzene to give the pure product (5.61g, 85%
yield).
a
Conditions: Perfluoroalkyl iodides (1.5 equiv.), olefin (1.0
equiv.), Na2S2O4 (1.5 equiv.), NaHCO3 (1.5 equiv.) and S1 (0.03
equiv.) were stirred at room temperature in H2O. b Isolated yield;
equiv.＝equivalent(s).
Table 3 The reactions of perfluoroalkyl iodides with alkynes in
watera
1H NMR (CDCl3, 300 MHz) δ: 1.31 (t, J＝7.4 Hz,
12H), 3.30 (q, J＝7.4 Hz, 8H); 19F NMR (CDCl3, 376
MHz) δ: −125.4 (s, 2F), −122.2 (s, 2F), −121.4 (s, 2F),
−120.2 (s, 2F), −118.0 (s, 2F), −82.9 (s, 2F), −81.7－
−82.4 (m, 2F), −67.9－−68.3 (m, 2F). Anal. calcd for
C16H20ClF16NO4S: C 29.01, H 3.02, N 2.11, F 45.93;
found C 28.79, H 3.16, N 2.13, F 45.85.
R2
RF
Na2S2O4/NaHCO3/surfactant
R2
RFI
+
H2O, 50 oC, 24 h
H
I
1
4
5
a RF = n-C4F9 (a), ClCF2CF2CF2CF2 (b), R2 = Ph (a),
n-C6H13 (b), 4-FC6H4 (c), 2'-Pyridine (d)
Z/Eb
－
Product
5aa
Yieldc/%
trace
71
Synthesis of Cl(CF2)6O(CF2)2SO3K (S2): To a solu-
tion of Cl(CF2)6O(CF2)2SO2F (5.38 g, 10 mmol) in
ethanol (15 mL) was added 2.7 mL KOH (7 mol/L) so-
lution. The mixture was then refluxed for 4 h. After the
system returned to room temperature, a lot of white
solid precipitated from the system. The residue was fil-
tered and then recrystallized in ethanol to give the pure
product (4.56 g, 80% yield). 19F NMR (CDCl3, 376
MHz) δ: −125.4－−125.6 (m, 2F), −122.2 (s, 2F),
−121.3－−121.6 (m, 2F), −120.2－−120.4 (m, 2F),
−118.2 (s, 2F), −82.8－−83.1 (m, 2F), −81.9－−82.0 (m,
2F), −68.9 (t, J ＝17.9 Hz, 2F). Anal. calcd for
C8ClF16KO4S: C 16.82, H 0, F 53.27; found C 16.82, H
0.3, F 53.01.
Entry RFI Alkyne
1d
1a
1a
1a
1a
1a
1b
4a
4a
4b
4c
4d
4a
2
3
4
5
6
1/5
5aa
1/20
1/15
1/10
1/15
54
5ab
71
5ac
83
5ad
62
5ba
a
Conditions: Perfluoroalkyl iodides (1.5 equiv.), alkynes (1.0
equiv.), Na2S2O4 (1.5 equiv.), NaHCO3 (1.5 equiv.) and S1 (0.03
equiv.) were stirred at 50 ℃ in H2O. b Determined by 19F NMR.
c Isolated yield. d At room temperature; equiv.＝equivalent(s).
Synthesis of CF3(CF2)6CH2CH2SO3Na (S3): To a
solution of CF3(CF2)6CH2CH2I (5.24 g, 10 mmol) in
ethanol (10 mL) was added 2.0 mL acetic acid and
KSCN (1.5 g, 15 mmol). The mixture was then refluxed
Conclusions
In summary, a new fluorinated surfactant was pre-
pared, characterized and applied to the fluoroalkylation
Chin. J. Chem. 2013, 31, 939—944
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941

Xiao et al.
FULL PAPER
for 12 h. The mixture was cooled to 60 ℃ and solids
were removed by a medium fritted glass filter. The sol-
vent was removed by evaporation under reduced pres-
sure. The crude product was washed with 20 mL warm
(50 ℃) water and then heated at 50 ℃ with 2 mL of
15 mol/L nitric acid for 10 h. After an additional 5 h at
85 ℃, the mixture was cooled to room temperature and
neutralized with saturated NaHCO3. The white solid
was collected and washed with acetone and yield 2.8 g
HRMS calcd for C10H12F9I 429.9840, found 429.9837.
(3,3,4,4,5,5,6,6,6-Nonafluoro-1-iodohexyl)cyclo-
hexane (3ad) 1H NMR (CDCl3, 400 MHz) δ: 0.78－
0.85 (m, 1H), 1.05－1.45 (m, 5H), 1.62－1.90 (m, 5H),
2.77－2.89 (m, 2H), 4.34 (dt, J＝10.4, 3.6 Hz, 1H); 19F
NMR (CDCl3, 376 MHz) δ: −131.4－−131.2 (m, 2F),
−120.4 and −118.3 (AB system, J＝274.8 Hz, 2F),
−86.5 (t, J＝9.4 Hz, 3F); IR (neat) νmax: 2931, 2857,
1452, 1350, 1236, 1135, 880, 738, 731, 584 cm−1; MS
m/z (relative intensity): 456 (M＋, 0.12), 329 (100), 287
(55.69), 69 (7.7). HRMS calcd for C12H14F9I 455.9997,
found 456.0001.
5,5,6,6,7,7,8,8,8-Nonafluoro-3-iodooctyl-4-methyl-
benzenesulfonate (3ae) 1H NMR (CDCl3,400 MHz) δ:
1.99－2.04 (m, 1H), 2.14－2.24 (m, 1H), 2.45 (s, 3H),
2.64－2.99 (m, 2H), 4.11－4.33 (m, 3H), 7.35 (d, J＝
8.0 Hz, 2H), 7.80 (d, J＝8.0 Hz, 2H); 19F NMR (CDCl3,
376 MHz) δ: −126.1－−125.8 (m, 2F), −124.7－−124.5
(m, 2F), −114.4 and −111.7 (AB system, J＝270.8 Hz,
2F), −81.0 (t, J＝9.4 Hz, 3F); IR (KBr) νmax: 2958, 1459,
1429, 1353, 1217, 1177, 1134, 1098, 1040, 978, 921,
841, 778, 736, 666, 588, 556, 533 cm−1. HRMS calcd
for C15H14O3F9S (M＋-I) 445.0520, found 445.0515.
1,1,1,2,2,3,3,4,4,5,5,6,6-Tridecafluoro-8-iododode-
cane (3bb) 1H NMR (CDCl3, 400 MHz) δ: 0.93 (t,
J＝7.2 Hz, 3H), 1.27－1.50 (m, 4H), 1.72－1.87 (m,
2H), 2.66－2.99 (m, 2H), 4.28－4.37 (m, 1H); 19F NMR
(CDCl3, 376 MHz) δ: −126.2－−126.1 (m, 2F), −123.7－
−123.6 (m, 2F), −123.0－−122.8 (m, 2F), −121.9－
−121.7 (m, 2F), −114.5 and −111.8 (AB system, J＝
1
(55%) of product as monohydrate. H NMR (DMSO,
400 MHz) δ: 2.40－2.54 (m, 2H), 2.61－2.65 (m, 2H);
19F NMR (DMSO, 376 MHz) δ: −125.5－−125.9 (m,
2F), −123.3－−123.7 (m, 2F), −122.7 (s, 2F), −121.7－
−121.9 (m, 2F), −113.1 (q, J＝15.9 Hz, 2F), −80.3 (t,
J＝10.2 Hz, 3F).
Typical procedure for the reaction of 1 with 2
Perfluorobutyl iodide (1a) (1.55 g, 4.5 mmol),
1-octene (2a) (0.33 g, 3 mmol), sodium dithionite (0.78
g, 4.5 mmol), sodium hydrogencarbonate (0.38 g, 4.5
mmol), S1 (60 mg, 0.09 mmol) and water (9 mL) were
stirred at room temperature for 12 h. Then 20 mL of
water was added. The mixture was extracted with ethyl
acetate (25 mL×3). The combined organic layer was
washed with saturated brine solution and dried over so-
dium sulfate. After removal of ethyl acetate, the residue
was purified over silica gel by chromatography to give
1,1,1,2,2,3,3,4,4-nonafluoro-6-iodododecane (3aa) as
colorless oil (1.23 g, yield 90%).
1,1,1,2,2,3,3,4,4-Nonafluoro-6-iodododecane (3aa)
1H NMR (CDCl3, 400 MHz) δ: 0.89 (t, J＝6.4 Hz, 3H),
1.25－1.56 (m, 8H), 1.72－1.85 (m, 2H), 2.68－2.99
(m, 2H), 4.27－4.36 (m, 1H); 19F NMR (CDCl3, 376
MHz) δ: −126.0－−125.9 (m 2F), −124.7－−124.5 (m,
2F), −114.9 and −112.0 (AB system, J＝273.7 Hz, 2F),
−81.1 (t, J＝9.4 Hz, 3F); IR (neat) νmax: 2960, 2932,
2860, 1486, 1351, 1235, 1136, 880, 723 cm−1; MS m/z
(relative intensity): 458 (M＋, 0.18), 331 (32.57), 289
(56.31), 57 (100), 43 (51.67).
1,1,1,2,2,3,3,4,4-Nonafluoro-6-iododecane (3ab)
1H NMR (CDCl3, 400 MHz) δ: 0.93 (t, J＝7.2 Hz, 3H),
1.25－1.51 (m, 4H), 1.72－1.87 (m, 2H), 2.68－2.99
(m, 2H), 4.27－4.36 (m, 1H); 19F NMR (CDCl3, 376
MHz) δ: −126.0－−125.8 (m, 2F), −124.7－−124.5 (m,
2F), −114.9 and −112.1 (AB system, J＝283.2 Hz, 2F),
−81.0 (t, J＝9.4 Hz, 3F); IR (neat) νmax: 2970, 1472,
1372, 1356, 1235, 1135, 881, 747, 716 cm−1; MS m/z
(relative intensity): 429 (M＋, 0.18), 303 (100), 69 (13.5),
43 (20.18).
1,1,1,2,2,3,3,4,4-Nonafluoro-6-iodo-7,7-dimethyl-
octane (3ac) 1H NMR (CDCl3, 400 MHz) δ: 1.10 (s,
9H), 2.69－3.05 (m, 2H), 4.17 (dd, J＝8.8, 7.2 Hz, 1H) ;
19F NMR (CDCl3, 376 MHz) δ: −125.9 (dt, J＝16.2,
15.0 Hz, 2F), −124.7 (d, J＝9.8 Hz, 2F), −116.0 and
−114.6 (AB system, J＝270.7 Hz, 2F), −81.0 (t, J＝9.4
Hz, 3F); IR (neat) νmax: 2970, 1470, 1371, 1356, 1235,
1135, 1092, 881, 847, 747, 705, 588 cm−1; MS m/z
(relative intensity): 303 (100), 69 (14.37), 43 (21.88).
276.5 Hz, 2F), −80.8 (t, J＝9.4 Hz, 3F); IR (neat) νmax
:
2963, 2935, 2864, 1476, 1363, 1239, 1145, 1078, 821,
732, 698, 657 cm−1; MS m/z (relative intensity): 530
(M＋, 0.16), 403 (100), 69 (9.69), 55 (7.81), 43 (27.83).
5,5,6,6,7,7,8,8,9,9,10,10,10-Tridecafluoro-3-iodo-
decan-1-ol (3bf) 1H NMR (CDCl3, 400 MHz) δ:
1.96－2.08 (m, 2H), 2.79－3.05 (m, 2H), 3.75－3.93
(m, 2H), 4.48－4.56 (m, 1H); 19F NMR (CDCl3, 376
MHz) δ: −126.2－−126.1 (m, 2F), −123.7－−123.6 (m,
2F), −123.0－−122.8 (m, 2F), −121.9－−121.7 (m, 2F),
−114.4 and −111.7 (AB system, J＝278.6 Hz, 2F),
−80.8 (t, J＝9.8 Hz, 3F); IR (neat) νmax: 3346, 2935,
1430, 1368, 1237, 1192, 1144, 1038, 888, 787, 701, 657,
531 cm−1; MS m/z (relative intensity): 518 (M＋, 3.82),
391 (100), 373 (45.45), 341 (52.51), 69 (40.81), 57
(54.8), 41 (30.52).
1-Chloro-1,1,2,2,3,3,4,4-octafluoro-6-iodododecane
(3ca) 1H NMR (CDCl3, 400 MHz) δ: 0.89 (t, J＝6.4
Hz, 3H), 1.24－1.46 (m, 8H), 1.70－1.87 (m, 2H),
2.67－2.99 (m, 2H), 4.29－4.36 (m, 1H); 19F NMR
(CDCl3, 376 MHz) δ: −123.0 (t, J＝13.5 Hz, 2F),
−119.9 －−119.7 (m, 2F), −114.7 and −111.6 (AB
system, J＝278.9 Hz, 2F), −68.1 (t, J＝12.0 Hz, 2F); IR
(neat) νmax: 2960, 2931, 2859, 1458, 1379, 1189, 1135,
967, 837, 795, 720, 701 cm−1; MS m/z (relative
intensity): 474 (M＋, 0.45), 347 (65.74), 305 (100), 57
(91.78), 43 (44.85).
942
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© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2013, 31, 939—944

Radical Addition of Perfluoroalkyl Iodides to Alkenes and Alkynes Initiated by Sodium Dithionite
(6-Chloro-3,3,4,4,5,5,6,6-octafluoro-1-iodohexyl)-
cyclohexane (3cd) 1H NMR (CDCl3, 400 MHz) δ:
0.78－0.85 (m, 1H), 1.05－1.45 (m, 5H), 1.62－1.90
(m, 5H), 2.77－2.89 (m, 2H), 4.34 (dt, J＝10.4, 3.6 Hz,
1H); 19F NMR (CDCl3, 376 MHz) δ: −123.0 (t, J＝12.0
Hz, 2F), −119.8 (dt, J＝17.7, 15.0 Hz, 2F), −114.8 and
−112.7 (AB system, J＝271.2 Hz, 2F), −68.1 (t, J＝12.0
Hz, 2F); IR (neat) νmax: 2930, 2856, 1451, 1368, 1256,
1189, 1135, 972, 839, 746, 727, 704 cm−1; MS m/z
(relative intensity): 472 (M＋, 0.14), 345 (100), 303
(60.83), 69 (12.89), 55 (23.85), 41 (8.9). HRMS calcd
for C12H14F8ClI 471.9701, found 471.9703.
1,1,2,2-Tetrafluoro-2-((1,1,2,2,3,3,4,4-octafluoro-
6-iodododecyl)oxy)ethanesulfonyl fluoride (3da) 1H
NMR (CDCl3, 400 MHz) δ: 0.88 (t, J＝6.4 Hz, 3H),
1.20－1.46 (m, 8H), 1.69－1.87 (m, 2H), 2.68－2.99
(m, 2H), 4.27－4.36 (m, 1H); 19F NMR (CDCl3, 376
MHz) δ: −121.1－−120.8 (m, 2F), −119.8 (s, 2F),
−110.7 and −107.9 (AB system, J＝268 Hz, 2F), −108.0
(s, 2F), −79.0－−78.8 (m, 2F), −77.9－−77.6 (m, 2F),
50.0 (s, 1F); IR (neat) νmax: 2960, 2932, 2860, 1465,
1355, 1322, 1211, 1150, 990, 820, 725, 609 cm−1; MS
m/z (relative intensity): 511 (24.61), 469 (47.73), 119
(100), 57 (82.03), 43 (39.08).
1,1,2,2-Tetrafluoro-2-((1,1,2,2,3,3,4,4-octafluoro-
6-iododecyl)oxy)ethanesulfonyl fluoride (3dg) 1H
NMR (CDCl3, 400 MHz) δ: 0.95 (t, J＝7.2 Hz, 3H),
1.37－1.64 (m, 2H), 1.65－1.87 (m, 2H), 2.67－2.99
(m, 2H), 4.28－4.37 (m, 1H); 19F NMR (CDCl3, 376
MHz) δ: −121.0－−120.8 (m, 2F), −119.8 (s, 2F),
−110.6 and −108.1 (AB system, J＝278 Hz, 2F), −108.2
(s, 2F), −79.0－−78.8 (m, 2F), −77.8－−77.6 (m, 2F),
50.1 (s, 1F); IR (neat) νmax: 2966, 2938, 2879, 1466,
1353, 1322, 1211, 1150, 991, 877, 821, 733, 650, 609
cm−1; MS m/z (relative intensity): 595 (M＋, 0.06), 469
(100), 119 (83.85), 67 (28.36), 55 (15.07). HRMS calcd
for C11H10F13IO3S 595.9188, found 595.9184.
(29.71), 152 (26.68), 102 (30.81).
1,1,1,2,2,3,3,4,4-Nonafluoro-6-iodododec-5-ene
(5ab) 1H NMR (CDCl3, 400 MHz) δ: 0.89 (t, J＝6.8
Hz, 3H), 1.24－1.38 (m, 6H), 1.52－1.63 (m, 2H), 2.58
－2.67 (m, 2H), 6.31 (t, J＝14.8 Hz, 1H); 19F NMR
(CDCl3, 376 MHz) δ: −126.0－−125.9 (m, 2F), −124.4－
−124.3 (m, 2F), −105.8－−105.7 (m, 2F), −81.2 (t, J＝
8.3 Hz, 3F); IR (neat) νmax: 2960, 2933, 2861, 1635,
1458, 1353, 1236, 1136, 1104, 1033, 881, 740, 695 cm−1;
MS m/z (relative intensity): 456 (1.68), 386 (27.62), 329
(15.76), 287 (19.27), 70 (25.82), 55 (22.24), 43 (100).
1-Fluoro-4-(3,3,4,4,5,5,6,6,6-nonafluoro-1-iodo-
hex-1-en-1-yl)benzene (5ac) 1H NMR (CDCl3, 400
MHz) δ: 6.60 (t, J＝13.6 Hz, 1H), 7.02 (t, J＝8.0 Hz,
2H), 7.28 (t, J＝8.0 Hz, 2H); 19F NMR (CDCl3, 376
MHz) δ: −126.0－−125.8 (m, 2F), −123.9－−123.8 (m,
2F), −111.0－−110.9 (m, 1F), −105.5－−105.4 (m, 2F),
−81.1 (t, J＝9.4 Hz, 3F); IR (neat) νmax: 2926, 1637,
1600, 1506, 1352, 1236, 1134, 1027, 892, 838, 750, 722
cm−1; HRMS calcd for C12H5F10I 465.9276, found
465.9272.
2-(3,3,4,4,5,5,6,6,6-Nonafluoro-1-iodohex-1-en-1-
yl)pyridine (5ad) 1H NMR (CDCl3, 400 MHz) δ: 6.67
(t, J＝13.6 Hz, 1H), 7.21－7.25 (m, 1H), 7.31 (d, J＝
8.0 Hz, 1H), 7.61－7.75 (m, 1H), 8.62－8.66 (m, 1H);
19F NMR (CDCl3, 376 MHz) δ: −126.0－−125.8 (m,
2F), −123.8－−123.6 (m, 2F), −106.2－−106.0 (m, 2F),
−81.0 (t, J＝9.8 Hz, 3F); IR (neat) νmax: 3057, 2927,
2856, 1640, 1583, 1568, 1464, 1430, 1352, 1235, 1134,
1027, 874, 741, 695 cm−1.
(6-Chloro-3,3,4,4,5,5,6,6-octafluoro-1-iodohex-1-
en-1-yl)benzene (5ba) 1H NMR (CDCl3, 400 MHz) δ:
6.59 (t, J＝13.6 Hz, 1H), 7.05－7.45 (m, 5H); 19F NMR
(CDCl3, 376 MHz) δ: −122.2－−122.2 (m, 2F), −119.8－
−119.5 (m, 2F), −105.5－−105.2 (m, 2F), −68.1 (t, J＝
12.0 Hz, 2F); IR (neat) νmax: 3055, 2960, 1635, 1445,
1309, 1192, 1134, 977, 842, 778, 694, 672 cm−1.
1,1,2,2-Tetrafluoro-2-((1,1,2,2,3,3,4,4-octafluoro-
6-iodo-8-methylnonyl)oxy)ethanesulfonyl
fluoride
Acknowledgments
(3dh) 1H NMR (CDCl3, 400 MHz) δ: 0.87 (d, J＝6.4
Hz, 3H), 0.97 (d, J＝6.4 Hz, 3H), 1.34－1.44 (m, 1H),
1.75－1.99 (m, 2H), 2.67－3.42 (m, 2H), 4.23－4.32
(m, 1H); 19F NMR (CDCl3, 376 MHz) δ: −121.2－
−120.9 (m, 2F), −119.6 (s, 2F), −110.4 and −108.0 (AB
system, J＝265 Hz, 2F), −108.2 (s, 2F), −79.1－−78.9
(m, 2F), −77.8－−77.6 (m, 2F), 50.0 (s, 1F); IR (neat)
νmax: 2962, 2876, 1463, 1389, 1354, 1321, 1208, 991,
877, 821, 741, 650, 609 cm−1; MS m/z (relative inten-
sity): 483 (100), 119 (64.21), 43 (67.39). HRMS calcd
for C12H12F13O3S (M−I) 483.0300, found 483.0302.
(3,3,4,4,5,5,6,6,6-Nonafluoro-1-iodohex-1-en-1-yl)-
benzene (5aa) 1H NMR (CDCl3, 400 MHz) δ: 6.58 (t,
J＝13.6 Hz, 1H), 7.04－7.48 (m, 5H); 19F NMR (CDCl3,
376 MHz) δ: −125.9－−125.8 (m, 2F), −123.9－−123.7
(m, 2F), −105.8－−105.7 (m, 2F), −81.0 (t, J＝8.3 Hz,
3F); IR (neat) νmax: 3063, 2927, 1636, 1489, 1445, 1352,
1235, 1134, 1028, 888, 756, 695, 591 cm−1; MS m/z
(relative intensity): 448 (M＋, 1.67), 321 (100), 182
We are grateful for the financial support from the
973 Program of China (No. 2012CB821600), the Na-
tional Natural Science Foundation of China (Nos.
21172241, 21032006) and the Science and Technology
Commission
of
Shanghai
Municipality
(No.
11ZR1445700).
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Chin. J. Chem. 2013, 31, 939—944