An efficient synthesis of perfluoroalkenylated aryl compounds via Pincer-Pd catalyzed Heck couplings

Article abstract of DOI:10.1016/j.jfluchem.2012.12.009

Heck couplings of aryl halides with fluoroalkyl-substituted ethylenes catalyzed by Pincer Palladium complex were described. A variety of fluorous ponytail-substituted aromatics were obtained with moderate to excellent yields. Moreover, the catalyst can be easily separated from the reaction mixture by F-SPE technique and reused three times without significant loss of activity.

Full text of DOI:10.1016/j.jfluchem.2012.12.009

Journal of Fluorine Chemistry 146 (2013) 6–10
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
An efficient synthesis of perfluoroalkenylated aryl compounds via Pincer-Pd
catalyzed Heck couplings
*
Jie Feng, Chun Cai
Chemical Engineering College, Nanjing University of Science & Technology, 200 Xiaolingwei, Nanjing 210094, PR China
A R T I C L E I N F O
A B S T R A C T
Article history:
Heck couplings of aryl halides with fluoroalkyl-substituted ethylenes catalyzed by Pincer Palladium
complex were described. A variety of fluorous ponytail-substituted aromatics were obtained with
moderate to excellent yields. Moreover, the catalyst can be easily separated from the reaction mixture by
F-SPE technique and reused three times without significant loss of activity.
Received 10 September 2012
Received in revised form 3 December 2012
Accepted 19 December 2012
Available online 27 December 2012
ß 2013 Elsevier B.V. All rights reserved.
Keywords:
Pincer Palladium
Fluoroalkyl-substituted ethylenes
Heck couplings
F-SPE
1. Introduction
the Herrmann–Beller catalyst to catalyze the Heck reaction between
perfluoroalkenes and aryl halides. However, Herrmann–Beller
Aromatic compounds bearing long fluoroalkyl chains are
widely used in fluorine chemistry and organic synthesis [1–3],
which have several unique properties compared with conventional
organic compounds including thermally stability, high chemical
inertness and, very particularly, low solubility in a large range of
common organic solvents because of low van der Waals
interactions.
There is an increasing demand for effective methods to
synthesize a large variety of perfluoroalkyl-substituted compounds.
To our best of knowledge, only a few reports have dealt with the
preparation of aromatic compounds bearing fluorous ponytails. A
successful method is based on the copper-mediated cross-couplings
of perfluoroalkyl iodides with aryl halides to synthesize a series of
perfluoroalkylated aromatic compounds [4–6]. This method gener-
ally results in limited yields because of the formation of fluorous by-
products which are difficult to remove. Ullmann-type couplings
between aryl bromidesor iodides and perfluoroalkyl iodides arealso
effective to the synthesis of thesecompounds, but excess copper and
harsh conditions are required [7,8].
catalyst inhibits the reactions involving aryl iodides.
Recently, Pincer complexes have become one kind of the most
successful catalysts in organic synthesis [11–17]. Meanwhile, due
to their unique tridentate coordination architecture, the Pincer
complex is stable, highly selective, highly active to ensure high
turnover numbers, and it permits low catalyst loadings and gives
the possibility for fine-tuning the catalytic properties of the metal
center [18].
In continuation of our studies in the research of cross-coupling
reactions [19–22], herein, we report an efficient PCP-Pincer
catalyst for the Heck couplings between perfluoroalkenes and
aryl halides. The Pincer Palladium catalyst can be easily prepared,
and the reactions of both aryl iodides and aryl bromides with
perfluoroalkenes in DMF are all proceeded smoothly to generate
the desired products in moderate to excellent yields. The double
bond of perfluoroalkyl-substituted aromatic compounds could be
further hydrogenated under standard conditions (1 mol% of Pd/C,
1 atm of H2). Furthermore, the catalyst can be easily separated
from the reaction mixture by F-SPE technique [23–26] and reused
three times without significant loss of its activity.
Sylvain et al. [9] have developed a new approach to yield
perfluoroalkyl-substituted aromatic compounds by Heck reaction
between perfluoroalkenes and arenediazonium salts in high yields.
But arenediazonium salts are unstable, which should be freshly
prepared before further use. Weiping Chen et al. [10] have employed
2. Results and discussions
The procedures for the synthesis of the catalyst were shown in
Scheme 1. The Pincer ligand was easily prepared using 1,3-
phenylenediamine and diphenylphosphinyl chloride as raw
materials with 4-dimethylamiopryidine as catalyst, and then
followed by ligand substitution reactions using the Pincer ligand
* Corresponding author. Tel.: +86 25 84315514; fax: +86 25 84315030.
E-mail address: c.cai@mail.njust.edu.cn (C. Cai).
0022-1139/$ – see front matter ß 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2012.12.009

J. Feng, C. Cai / Journal of Fluorine Chemistry 146 (2013) 6–10
7
Scheme 1. Preparation of the Pincer-Pd complex.
Table 1
Solvent study for the Heck reaction of iodobenzene with 1H,1H,2H-Perfluoro-1-octene.a
.
Entry
Solvent
Base
Time (h)
Temperature (8C)
Yield (%)b
1c
2
EtOH:H2O (v/v) = 1:1
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
24
24
24
24
24
24
110
110
80
80
H2O
5
3
CH3CN
DMSO
H2O
None
43
91
94
4
110
110
110
5c
6
DMF
a
Reaction conditions: iodobenzene (1.0 mmol), 1H,1H,2H-Perfluoro-1-octene (1.1 mmol), base (1.0 mmol), catalyst (1 mol%), 2 mL DMF, in air.
b
c
GC yield.
TBAB was added.
Table 2
Time and temperature study for the Heck reaction of iodobenzene with 1H,1H,2H-Perfluoro-1-octene.a
.
Entry
X
Base
Time (h)
Temperature (8C)
Yield (%)b
1
2
3
4
5
6
I
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
24
24
24
24
72
72
100
110
120
130
120
130
83
94
75
18
40
52
I
I
Br
Br
Br
a
Reaction conditions: aryl halide (1.0 mmol), 1H,1H,2H-Perfluoro-1-octene (1.1 mmol), base (1.0 mmol), catalyst (1 mol%), 2 mL DMF, in air.
b
GC yield.
with Pd(COD)Cl2 to give the catalyst in the yield of 90%, which was
isolated as yellow solid [27,28].
The ligand and the catalyst were characterized by IR spectra and
NMR spectra. All results were in full agreement with the proposed
structure.
iodobenzene converted in 24 h. However, as for bromobenzene,
the best reaction temperature is 130 8C, and the reaction time
prolongs to 72 h (Table 2, entry 6).
The effect of bases was also examined for this Heck reaction.
K3PO4 was found to be the most effective base (Table 3, entry 1).
Slightly lower yields were obtained when K2CO3, NaOAc, and
Na2CO3 were used as base (Table 3, entries 2, 3, and 5). When the
organic bases Et3N was used, only moderate yield was obtained
(Table 3, entry 4).
To evaluate the catalytic activity of the Pincer-Pd catalyst in the
Heck couplings between aryl halides with fluoroalkyl-substituted
ethylenes, the reaction between iodobenzene and 1H,1H,2H-
Perfluoro-1-octene in the presence of 1 mol% Pincer-Pd catalyst
was chosen as a model reaction. Various factors including solvent,
base, temperature and time were screened to optimize the reaction
conditions. The results are summarized in Tables 1–3.
Among the different solvent tested, DMF was the most
productive (Table 1, entry 6). This attributes to the good solubility
of catalyst in DMF, and makes the coupling reaction in a
homogeneous way. Lower catalyst activities were found in other
solvents such as DMSO, CH3CN and water (Table 1, entries 2–4).
However, when tetrabutylammonium bromide (TBAB) was added
as phase transfer catalyst, water proved to be effective (Table 1,
entry 5).
The optimized conditions were applied to different aryl halides
and
perfluoroalkenes
(CH255CHC4F9,
CH255CHC6F13
and
CH255CHC8F17) to survey the generality of the catalytic protocol.
The results are listed in Table 4.
As can be seen from Table 4, a variety of aromatic halides
underwent Heck couplings smoothly to afford a wide range of
perfluoroalkenylated aromatic compounds. Aryl iodides show high
activity in the couplings (Table 4, entries 1–10) which attributes to
aryl iodide’s high reaction activity and Pincer complex’s unique
tridentate coordination architecture. Only one free coordination site
isavailableforcatalysis, which impliesthatformationofundesirable
side products arising from ligandexchange processescan beavoided
[29]. It was also found that aryl iodides bearing electron-
withdrawing substituent afforded the corresponding coupling
product in better yields than electron-donating substituent in para
Then, we took the temperature into consideration. As illustrat-
ed in Table 2, entries 1–3, 110 8C is the best temperature for the
Heck couplings between iodobenzene and 1H,1H,2H-Perfluoro-1-
hexene. The proceedings of the reactions were traced by GC, most of

8
J. Feng, C. Cai / Journal of Fluorine Chemistry 146 (2013) 6–10
Table 3
Base study for the Heck reaction of iodobenzene with 1H,1H,2H-Perfluoro-1-octene.a
.
Entry
Solvent
Base
Time (h)
Temperature (8C)
Yield (%)b
1
2
3
4
5
DMF
DMF
DMF
DMF
DMF
K3PO4
K2CO3
NaOAc
NEt3
24
24
24
24
24
110
110
80
91
92
88
77
90
110
110
Na2CO3
a
Reaction conditions: aryl halide (1.0 mmol), 1H,1H,2H-Perfluoro-1-octene (1.1 mmol), base (1.0 mmol), catalyst (1 mol%), 2 mL DMF, in air.
b
GC yield.
Table 4
Heck cross-coupling reactions of aryl halides with fluoroalkyl-substituted ethylenes.a
.
Entry
R
X
Rf
Time (h)
Temp (8C)
Yield (%)b
E/Zd
1
2
H
I
n-C6F13
n-C6F13
n-C6F13
n-C6F13
n-C6F13
n-C6F13
n-C6F13
n-C6F13
n-C4F9
24
24
24
24
24
24
24
24
24
24
72
72
72
48
72
72
12
12
12
12
48
24
110
110
110
110
110
110
110
110
110
110
130
130
130
130
130
130
130
130
130
130
130
135
95
90:10
83:17
87:13
90:10
91:9
92:8
85:15
–
4-OCH3
4-CH3
3-CH3
2-CH3
4-Br
I
79
3
I
89
4
I
93
5
I
84
6
I
91
7
4-Cl
I
93
8
4-NO2
H
I
10 (50c)
94
9
I
87:13
91:9
77:23
94:6
–
10
11
12
13
14
15
16
17
18
19
20
21
22
H
I
n-C8F17
n-C6F13
n-C6F13
n-C6F13
n-C6F13
n-C6F13
n-C8F17
n-C6F13
n-C6F13
n-C4F9
90
H
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Cl
61
4-OCH3
4-NO2
4-CF3
2-CH3
4-OCH3
3-CHO
4-CHO
4-CHO
4-CHO
4-COCH3
4-CHO
40
49 (45c)
79
91:9
88:12
86:14
88:12
95:5
90:10
96:4
89:11
84:16
57
50
90
93
87
n-C8F17
n-C6F13
n-C6F13
93
87
27
a
Aryl halides (1.0 mmol), fluoroalkyl-substituted ethylenes (1.1 mmol), base (1.0 mmol), catalyst (1 mol%) in 2 mL DMF at 110–130 8C in air.
Isolated yield.
b
c
Dehalogenation product.
Determined by GC.
d
or ortho position (Table 4, entries 1–7). This electronic effect is not
As for aryl bromides, the compounds with electron-withdraw-
ing groups, especially the bromides substituted aromatic alde-
hydes, reacted smoothly, while aryl bromides with electron-
donating groups were less reactive (Table 4, entries 11–18),
unsatisfactory yields were obtained even after prolonged reaction
times to 72 h.
surprising, sincetheoxidativeadditionoftheC–Ibondofaryliodides
to the metal is expected to be facilitated by electron-withdrawing
substituentonthearomaticring[30]. Howeverthenitro-substituted
iodobenzeneisa exception affording moredehalogenations thanthe
aimed products (Table 4, entry 8).
Scheme 2. A potential application of Pincer-Pd catalyzed Heck couplings.

J. Feng, C. Cai / Journal of Fluorine Chemistry 146 (2013) 6–10
9
100
90
80
70
60
50
40
30
20
10
0
an Agilent 7890A instrument (Column: Agilent 19091J-413: 30 m ꢀ
320 m, carrier gas: N2, Injector: 300 8C, FID detection
mm ꢀ 0.25
m
catalyst reuse+10%
new catalyst
detector: initial temperature 80 8C, temperature program: 15 8C/
min, final temperature 325 8C. H2 30 mL/min, air 400 mL/min, N2
25 mL/min). Melting points were determined uncorrected. 1H NMR
was recorded on Bruker DRX 500 and tetramethylsilane (TMS) was
used as a reference.
catalyst reuse
catalyst first use
4.2. Preparation of N,N-Bis (diphenylphosphino)-1,3-benzenediamine
(PCP-Pincer)
first use
1
2
3
Run
To a suspension of 1,3-diaminobenzene (2.5 g, 23 mmol) in
toluene (50 mL) was added triethylamine (5.6 mL, 46 mmol), 4-
dimethylamiopryidine (0.28 g, 2.3 mmol). The mixture was then
cooled to 0 8C, PPh2Cl (10.1 g, 46 mmol) was added in a dropwise
fashion, the solution was warmed to room temperature and stirred
at 80 8C for 12 h. After that, the solution was filtered and the
solvent was removed under vacuum. The remaining yellow oil was
purified by column chromatography and further purified by
recrystallization (toluene:hexane (v/v) = 1:1). Yield: 8.75 g (80%).
Fig. 1. Recycling experiments of the catalyst.
Regardless of aryl iodides or aryl bromides used as substrates,
the stereoselectivity of the products were found, and the trans-
isomers takes up 77–96%. The existing small amount cis-isomer
may come from (i) post-reaction isomerization of products, leading
to thermodynamically controlled mixture of isomers; (ii) isomeri-
zation of product Pd–H complex before the deprotonation takes
place [31].
In addition, the coupling reaction worked equally well with
both long and short fluorous olefins. Considering the electron
effect, space effect and volatility of different length of fluorous tails,
small difference of product yields were made (Table 4, entries 9, 10,
18–20).
We also examined whether aryl chlorides were active for the
Heck reaction in our system. However, lower conversions and
yields were obtained with aryl chlorides (Table 4, entry 22) just as
in other cases.
To further demonstrate the potential of this methodology,
fluoroalkenylated aryl phosphine oxide, a crucial intermediate en
route to a recyclable wilkinson catalyst [32], was smoothly
generated by the coupling of fluoroalkenyl-substituted ethylenes
with tris-(4-bromo-phenyl)-phosphane oxide (Scheme 2) in the
yield of 75%.
Melting point: 90–92 8C. IR (KBr);
n
3197, 3071, 1579, 1474, 1430,
1149, 1090, 978, 743, 694 cmꢁ1. 1H NMR (CDCl3):
d = 7.48–7.33 (m,
20H, PPh), 7.03 (t, J = 8.0 Hz, 1H, Ph4), 6.74 (t, J = 2.1 Hz, 1H, Phipso),
6.53 (d, J = 8.0 Hz, 2H, Ph3,5), 4.35 (d, J = 8.2 Hz, 2H, NH), (d,
J = 7.8 Hz, 1H, Ph4), 13C{1H} NMR (CDCl3):
d
= 147.5 (d, J = 16.5 Hz,
Ph), 140.0 (d, J = 11.9 Hz, CPPh), 131.1 (d, J = 20.7 Hz, CPPh), 130.0
(CPh), 128.9 (CPPh), 128.4 (d, J = 6.5 Hz, CPPh), 107.1 (d, J = 13.8 Hz,
Ar), 103.1 (t, J = 13.4 Hz, CAr).
C
C
4.3. Preparation of N,N-Bis (diphenylphosphino)-1,3-benzenediamine
(PCP-Pd)
Pd(COD)Cl2 (142 mg, 0.5 mmol) was added to a solution of PCP-
Pincer (227 mg, 0.5 mmol) in toluene (10 mL), and the mixture was
refluxed for 5 h, whereupon a yellow solid precipitated, which was
collected on a glass frit and washed with Et2O (10 mL ꢀ2). Yield:
The Pincer-Pd catalyst in this system can be separated from the
reaction mixture by F-SPE technique and reused several times
without significant loss of activity (Fig. 1). The slight decrease of
the yield may be due to the catalyst adsorption of fluorous silica gel
column and the loss in separation. The addition of fresh catalyst
added to each circle increased the level of conversion and the
resulting yields returned to that seen in the initial experiment.
350 mg (90%). IR (KBr);
1102, 765, 741 cmꢁ1 1H NMR (DMSO):
7.82 (m, 6H, PPh), 7.55–7.40 (m, 14H, PPh), 6.70 (t, J = 7.8 Hz, 1H,
Ph4),6.23(d, J = 7.8 Hz,2H,Ph3,5).13C{1H}NMR(DMSO):
= 156.7(t,
n
3211, 2588, 1599, 1542, 1454, 1434, 1386,
.
d
= 7.98 (s, 2H, NH), 7.90–
d
J = 14.1 Hz, CAr), 134.9 (t, J = 25.0 Hz, CPPh), 131.6 (t, J = 7.8 Hz, CPPh),
131.2 (CPPh), 129.0 (CAr), 128.8 (t, J = 5.2 Hz, CPPh), 103.0 (t,
J = 10.1 Hz, CAr).
3. Conclusions
4.4. General procedures for Heck reactions using 1 mol% Pincer-Pd
complex
In summary, we have prepared and characterized a PCP Pincer-
Pd catalyst and successfully applied it for the Heck couplings
between perfluoroalkenes and aryl halides for the preparation of
perfluoroalkenylated aryl compounds. The catalyst showed high
catalytic activity and the corresponding coupling products were
obtained in moderate to excellent yields. Moreover, the catalyst
could be easily separated by F-SPE technique and reused three
times without significant loss of activity. The simple procedure for
catalyst preparation, high activity and reusability of the catalyst is
expected to contribute to its utilization for the development of
fluorine chemistry.
A
sealed tube was charged with aryl halide (1.0 mmol),
fluoroalkyl-substituted ethylenes (1.1 mmol), K3PO4 (1.0 mmol),
DMF (2 mL) and catalyst (1 mol% Pd), the mixture was stirred at a
certain temperature for a certain time. After being cooled to room
temperature, the mixture was filtered. The solvent and excess
fluoroalkyl-substituted ethylenes were removed under reduced
pressure and the residue was purified by F-SPE technique. Menthol
and H2O (v/v = 8:2) were used as fluorophobic elution, while H2O
were used as fluorophilic elution. The product was obtained from
fluorous phase in high purity. All the products were known
compounds and were identified by comparison of their physical
and spectroscopic data with those of authentic samples. Characteri-
zationdatasofsomerepresentativeexamplesaregivenasfollowing:
4. Experimental
4.1. General
(1) (3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoro-oct-1-enyl)-benzene
(Table 4, entry 1)
All the reagents were commercially available and used without
any further purification. The solvents were dried before use.
Colorless oil (0.39 g, 0.93 mmol), prepared from iodoben-
IR spectra were recorded in KBr disks with
a SHIMADZU
zene (0.2 g, 1 mmol) and 1H,1H,2H-Perfluoro-1-octene (0.38 g,
IRPrestige-21 FT-IR spectrometer. GC analyses were performed on

10
J. Feng, C. Cai / Journal of Fluorine Chemistry 146 (2013) 6–10
1.1 mmol) in 93% yield according to the general procedure. 1H
NMR (CDCl3): = 6.20 (dt; J = 16 Hz, 1H, CF2–CH); 7.17 (dt;
J = 16 Hz, 1H, Ar–CH); 7.36–7.60 (m; 5H, aromatic protons); 13
NMR (CDCl3): = 114.6 (t; J = 23 Hz; CH–CF2); 127.8 (s; CAr);
129.2 (s; CAr); 130.4 (s; CAr); 133.8 (s; CAr, ipso), 140.0 (t;
J = 10 Hz; Ar–CH). 19F NMR (CDCl3):
fluoro-1-octene (0.38 g, 1.1 mmol) in 72% yield according to the
general procedure. 1H NMR (CDCl3):
= 6.21 (dt; J = 16 Hz, 1H,
CF2–CH); 7.19 (dt; J = 16 Hz, 1H, Ar–CH); 7.30–7.60 (m; 4H,
aromatic protons); 13C NMR (CDCl3):
= 28.7 (s; CF3); 114.2 (t;
CH–CF2); 120.3 (s; CAr); 128.7 (s; CAr); 137.1 (s; CAr); 137.3 (s;
Ar), 148.2 (s; Ar–CF3). 19F NMR (CDCl3):
d
d
C
d
d
d
= ꢁ81.2 (t; J = 10.5 Hz,
C
d
= ꢁ57.8 (t; 3F);
3F); ꢁ111.5 (m; 2F); ꢁ122.0 (m; 2F); ꢁ123.2 (m; 2F); ꢁ123.6
ꢁ80.8 (t; 3F); ꢁ111.0 (m; 2F); ꢁ121.6 (m; 2F); ꢁ122.9 (m; 2F);
ꢁ123.3 (m; 2F); ꢁ126.2 (m; 2F).
(m; 2F); ꢁ126.6 (m; 2F).
(2) 1-(40-Bromophenyl)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-
1-ene (Table 4, entry 6)
4.5. A typical procedure for recycle and reuse of catalyst
White solid (0.45 g, 0.9 mmol), prepared from 1-bromo-4-
iodo-benzene (0.28 g, 1 mmol) and 1H,1H,2H-Perfluoro-1-
octene (0.38 g, 1.1 mmol) in 91% yield according to the general
A sealed tube was charged with 1H,1H,2H-Perfluoro-1-octene
(1.9 g, 5.5 mmol), iodobenzene (1 g, 5.0 mmol), K3PO4 (1.06 g,
5.0 mmol), DMF (10 mL) and Pincer-Pd catalyst (25 mg, 1 mmol%),
the mixture was stirred at 110 8C for 24 h. After being cooled to
room temperature, the mixture was separated by F-SPE technique.
Methanol and H2O (v/v = 8:2) were used as fluorophobic elution,
while methanol were used as fluorophilic elution. Then, the solvent
of fluorophobic phase was removed, and the resulting solids were
washed with Et2O (3ꢀ 15 mL) and dried under vacuum, yellow
solid (23 mg) was obtained. For the second run, fresh starting
materials, the catalyst obtained and extra fresh catalyst (2.5 mg,
10%) were added to the sealed tube, and the reaction was
conducted as described for the initial run. After 3 runs, the product
yields are respectively 91%, 89%, 87%.
procedure. Melting point: 28–30 8C. 1H NMR (CDCl3):
d = 6.22
(dt; 1H, J = 16.1 Hz, CF2–CH); 7.12 (dt; 1H, J = 16.1 Hz, Ar–CH);
7.36–7.57 (m; 4H, aromatic protons); 13C NMR (CDCl3):
d
= 115.0 (t; J = 23 Hz; CH–CF2); 124.4 (s; CAr); 129.0 (s; CAr);
132.1 (s; CAr); 132.4 (s; CAr), 138.5 (t; J = 9.5 Hz; Ar–CH). 19F
NMR (CDCl3):
d
= ꢁ80.8 (t; 3F); ꢁ111.3 (m; 2F); ꢁ122.8 (m;
2F); ꢁ123.1 (m; 2F); ꢁ123.2 (m; 2F); ꢁ126.2 (m; 2F).
(3) 1-Methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-oct-1-
enyl)-benzene (Table 4, entry 3)
Colorless oil (0.38 g, 0.87 mmol), prepared from 1-iodo-3-
methyl-benzene (0.22 g, 1 mmol) and 1H,1H,2H-Perfluoro-1-
octene (0.38 g, 1.1 mmol) in 89% yield according to the general
procedure. 1H NMR (CDCl3):
d
= 6.22 (dt; J = 16 Hz, 1H, CF2–CH);
7.17 (dt; J = 16 Hz, 1H, Ar–CH); 7.23–7.34 (m; 4H, aromatic
protons); 13C NMR (CDCl3):
= 20.3 (s; CH3); 113.0 (t; CH–CF2);
123.9 (s; CAr); 127.3 (s; CAr); 127.9 (s; CAr); 130.0 (s; CAr); 130.2
(s; CAr), 139.0 (t; Ar–CH). 19F NMR (CDCl3):
References
d
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732.
d
= ꢁ80.8 (t; 3F);
ꢁ111.4 (m; 2F); ꢁ121.6 (m; 2F); ꢁ123.2 (m; 4F); ꢁ126.2 (m; 2F).
(4) (3,3,4,4,5,5,6,6,6-Nonafluoro-hex-1-enyl)-benzene (Table 4,
entry 9)
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Colorless oil (0.3 g, 0.92 mmol), prepared from iodobenzene
(0.2 g, 1 mmol) and 1H,1H,2H-Perfluoro-1-hexene (0.27 g,
1.1 mmol) in 92% yield according to the general procedure.
1H NMR (CDCl3):
d
= 6.19 (dt; J = 16 Hz, 1H, CF2–CH); 7.17 (dt;
J = 16 Hz, 1H, Ar–CH); 7.30–7.60 (m; 5H, aromatic protons); 13
NMR (CDCl3): = 114.6 (t; CH–CF2); 127.4 (s; CAr); 128.8 (s;
Ar); 130.4 (s; CAr); 133.8 (s; CAr), 140.0 (t; Ar–CH). 19F NMR
(CDCl3):
C
d
C
d
= ꢁ81.2 (t; Hz, 3F); ꢁ111.7 (m; 2F); ꢁ124.6 (m; 2F);
ꢁ126.2 (m; 2F).
´
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(5) (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-dec-1-
enyl)-benzene (Table 4, entry 10)
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Colorless oil (0.46 g, 0.88 mmol), prepared from iodobenzene
(0.2 g, 1 mmol) and 1H,1H,2H-Perfluoro-1-heptene (0.49 g,
1.1 mmol) in 88% yield according to the general procedure. 1H
NMR (CDCl3):
J = 16 Hz, 1H, Ar–CH); 7.30–7.60 (m; 5H, aromatic protons); 13
NMR (CDCl3): = 114.6 (t; CH–CF2); 127.8 (s; CAr); 129.2 (s; CAr);
130.4 (s; CAr); 133.8 (s; CAr); 140.0 (t; Ar–CH). 19F NMR (CDCl3):
d = 6.19 (dt; J = 16 Hz, 1H, CF2–CH); 7.17 (dt;
C
d
d
= ꢁ81.2 (t; 3F); ꢁ111.5 (m; 2F); ꢁ122.0 (m; 2F); ꢁ122.4 (m;
4F); ꢁ123.2 (m; 2F); ꢁ123.6 (m; 2F); ꢁ126.6 (m; 2F).
(6) 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoro-oct-1-enyl)-4-tri-
fluoromethyl-benzene (Table 4, entry 14)
Colorless oil (0.35 g, 0.72 mmol), prepared from 1-bromo-4-
trifluoromethyl-benzene (0.23 g, 1 mmol) and 1H,1H,2H-Per-