Selective C4-F bond cleavage/C-O bond formation of polyfluoroarenes with phenols and benzyl alcohols

Article abstract of DOI:10.1016/j.jfluchem.2013.08.013

A facile and efficient S_NAr method for the synthesis of unsymmetrical polyfluoroaryl ethers via selective C4-F bond cleavage of pentafluorobenzene is reported. The reaction could proceed smoothly without the requirement of additional metals or ligands, and afford a series of the corresponding products in good to high yields. A wide variety of substituted phenols and alcohols provided 1,2,4,5-tetrafluoropheny ether derivatives in regioselective manner.

Full text of DOI:10.1016/j.jfluchem.2013.08.013

Journal of Fluorine Chemistry 156 (2013) 51–60
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Selective C4ÀF bond cleavage/CÀO bond formation of
polyfluoroarenes with phenols and benzyl alcohols
Cuibo Liu a, Liming Cao a, Xuguang Yin a, Haolan Xu b, Bin Zhang a,
*
a Department of Chemistry, School of Science, Tianjin University, The Co-Innovation Center of Chemistry and Chemcial Engineering of Tianjin, and The Key Lab
of Systems Bioengineering, Ministry of Education, Tianjin 300072, China
b Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095, Australia
A R T I C L E I N F O
A B S T R A C T
Article history:
A facile and efficient SNAr method for the synthesis of unsymmetrical polyfluoroaryl ethers via selective
C4–F bond cleavage of pentafluorobenzene is reported. The reaction could proceed smoothly without the
requirement of additional metals or ligands, and afford a series of the corresponding products in good to
high yields. A wide variety of substituted phenols and alcohols provided 1,2,4,5-tetrafluoropheny ether
derivatives in regioselective manner.
Received 24 June 2013
Received in revised form 24 August 2013
Accepted 28 August 2013
Available online 4 September 2013
ß 2013 Elsevier B.V. All rights reserved.
Keywords:
Polyfluoroarenes
C–F bond cleavage
C–O bond formation
Phenols
Benzyl alcohols
1. Introduction
electron affinity, which is necessary for the carbon–fluorine bond
breakage [9]. In other words, the fluorocarbons must be actived by
Aryl ethers and their derivatives are key intermediates in
organic chemistry and their importance as structural motifs has
been witnessed in a great number of natural products, polymer
industries, pharmaceuticals, which provide a strong motivation for
the developments of synthetic methodology [1]. Compounds with
the activating or directing atoms/groups. At present, there are
reports on the C–O bond formation via C–F bond cleavage of aryl
fluorides with phenols or alcohols [10], and usually the substrates
are associated with the activating or directing atoms/groups on the
aryl ring, such as nitro and cyano groups [11]. Pentafluoroarenes
are known as electron-deficient compounds and important
fluorine-containing compounds [12]. Because of the existence of
several fluorine atoms on aryl ring and its high electronegativity of
fluorine, we speculate that some of the carbon–fluorine bonds on
the aryl ring of the polyfluoroarenes may be attacked by the
electron-rich atoms or groups. To date, some strategies have
revealed the synthesis of polyfluorinated aromatic ethers via the
C–F cleavage of polyfluoroarenes, but they are suffering from some
drawbacks, such as complex reaction system, limited substrate
scope, lower yields, longer reaction time and so on [13]. Cao
reported a catalytic strategy for C–F bond cleavage of octafluor-
otoluene with arylboronic acids in the presence of Ni catalyst to
provide unsymmetrical biaryl ethers [14]. Additionally, Weng and
co-workers demonstrated a Pd/Ag co-catalystic system for the
access to polyfluorinated aromatic ethers [15]. Very recently, our
group has reported the synthesis of N-tetrafluoroarylated hetero-
cyclic compounds via selective C4–F bond cleavage of pentafluor-
obenzene with N–H containing heterocycles under mild conditions
[16]. It will be of special interest to extend this facile approach to
prepare polyfluorinated aromatic ethers. Although elegant work
a
polyfluorinated aromatic structure are useful moieties in
medicinal chemistry and material science [2]. Hence, synthesis
of polyfluorinated aromatic ethers is of high potential interest [3].
The Ullmann-type coupling reaction [4] and nucleophilic aromatic
substitution (SNAr) reaction [5] represent two classic methods for
the preparation of the aryl ethers. As alternate methodologies, such
as microwave and ultrasound assisted methods [6], use of metals
and/or noble metal nanoparticles as catalysts [7] and directed C–H
activation of aromatic compounds with alcohols [8] were also
emerged for the preparation of the aryl ethers. Although these
pioneering and intriguing works are very practical, yet, the
methods presented above are mainly focused on the substrates
of aryl chlorides, aryl bromides or aryl iodides reacting with
phenols or alcohols.
It is well known that fluorocarbons are prone to be attacked by
the electron-rich atoms or groups if the carbon atoms have a strong
*
Corresponding author. Tel.: +86 22 27406140; fax: +86 22 27403475.
E-mail address: bzhang@tju.edu.cn (B. Zhang).
0022-1139/$ – see front matter ß 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2013.08.013

52
C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
Scheme 1. Synthesis of polyfluorinated aromatic ethers.
Table 1
Synthesis of polyfluorinated diaromatic ethers derived from phenols with pentafluorobenzene.a
a
Reaction conditions: 1a (0.3 mmol), phenols (0.2 mmol) and Cs2CO3 (0.3 mmol) were added in DMSO (2.0 mL) with stirring at RT for 8 h. Yield: isolated yield.

C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
53
has been achieved, the development of a simple and efficient
method for the polyfluorinated aromatic ethers with the strategy
of C–F bond cleavage of polyfluoroarenes is highly desirable.
Herein, we report an operationally simple, effective and
transition metal-free SNAr reaction for the synthesis of unsymme-
trical polyfluoroaryl ethers via selective C–F bond cleavage of
pentafluorobenzene with a variety of phenols and benzyl alcohols
(Scheme 1). In the absence of additional metals or ligands, the
reaction could be carried out under mild conditions to afford a
series of O-polyfluoroarylated products in good to high yields. In
addition, our protocol was also applied to other polyfluoroarenes
and some long-chain aliphatic alcohols.
3). This result suggested that C4–F bond cleavage/C–O bond
formation occured under the ambient conditions, and showed that
our speculation on the attack of the electron-rich atoms or groups
to the carbon–fluorine bonds on the aryl ring of 1a was reasonable.
Note that no detectable amount of products via the other C–F
bonds cleavage of 1a was observed under our conditions, and thus
implying that our method gave highly selective products through
C4–F bond cleavage/C–O bond formation of pentafluorobenzene.
But, in the absence of Cs2CO3 while remaining other conditions
unchanged, no products were obtained even after 24 h at room
temperature. These results suggested that the base played an
important role in this SNAr reaction. Next, a survey of reaction
parameters including bases and solvents was carried out (Table S1
in the supporting information). After the screen of several bases, it
was found that Cs2CO3 gave the best yield in this interesting
reaction (Table S1, entries1, 2, 4–7). Subsequently, a broader
investigation of solvents suggested that DMF was less favorable
than DMSO and others were ineffective or useless for the synthesis
of polyfluoroaryl ethers (Table S1, entries 9–15). We also tested the
2. Results and discussion
Initially, pentafluorobenzene 1a was treated with 4-phenyl-
phenol 2 in the presence of 1.5 equiv Cs2CO3 in DMSO at room
temperature for 8 h. It was found that the corresponding
polyfluoroaryl ether was obtained in 85% yield (Table S1, entry
Table 2
O-Polyfluoroarylation of 4-phenylphenol with polyfluoroarenes.a
a
Reaction conditions: polyfluoroarenes (0.3 mmol), 4-phenylphenol (0.2 mmol) and Cs2CO3 (0.3 mmol) were added in DMSO (2.0 mL) with stirring at RT for 8 h. Yield:
isolated yield.
bThe reaction was conducted at 150 8C for 2 h.

54
C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
effect of temperature and found that a lower reaction temperature
resulted in a longer reaction time and lead to a lower conversion.
Elevation of the temperature did not show an obvious improve-
ment. Hence, the optical conditions for this reaction are that DMSO
as a solvent in combination with Cs2CO3 as a base at room
temperature works well for this O-polyfluoroarylation protocol.
Encouraged by the efficiency of the protocol described above,
the substrate scope was investigated. A variety of substituted
phenols were tested under the optimized conditions using 1a as
the polyfluoroarylating agent (Table 1). Gratifyingly, several
electron-rich phenols were suitable in this reaction to afford the
corresponding ethers in excellent yields (entries 3b, 3d, 3g, 3k–
3p). Phenols with electron withdrawing groups such as chlorine,
bromine at the different positions successfully reacted with 1a to
give the desired products in good yields (entries 3c, 3e, 3f, 3j).
Additionally, when cyano groups at the para-position of phenol led
to a slightly decreased yield (entry 3i). However, in the cases of the
substrate having nitro group (3h and 3r), the SNAr reaction did not
occur. This may be due to the strong electron-withdrawing
property of nitro group. The presence of a heteroatom in the
aromatic nucleus also provided the product in acceptable yield
(entry 3s). Either 1-naphthol or 2-naphthol was the suitable
partner in this O-polyfluoroarylation reaction (entries 3t, 3u).
Moreover, the di-substituted phenols did not hamper the reaction
and afforded the corresponding products in high yields (3p and
3q). These results further showed that our strategy gave highly
selective products through C4–F bond cleavage/C–O bond forma-
tion of polyfluorobenzene with phenols.
As an extension of this work, various polyfluoroarenes were
treated. The results are consistent with the above when reacted
octafluorotoluene, 2,3,4,5,6-pentafluorotoluene and hexafluoro-
benzene with 4-phenylphenol 2 and they all gave the desired
products (Table 2, entries 1–3), despite a moderate yield for
hexafluorobenzene (Table 2, entry 2). 1,2,4-Trifluorobenzene was
Table 3
Synthesize of polyfluorinated aromatic ethers derived from alcohols with pentafluorobenzene.a
a
Reaction conditions: 1a (0.3 mmol), alcohols (0.2 mmol) and Cs2CO3 (0.3 mmol) were added in DMSO (2.0 mL) with stirring at 60 8C for 18 h. Yield: isolated yield.

C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
55
Scheme 2. SNAr reaction of diphenols and triphenol with pentafluorobenzene.
also chosen as the investigated target for this reaction. Yet, the
result was obtained at elevated reaction temperature (150 8C)
rather than at room temperature (Table 2, entry 4). However,
mono-fluorobenzene and 1,4-difluorobenzene were not reactive
under the selected conditions (Table 2, entries 5, 6).
compounds via selective C–F bond cleavage/C–O bond
formation of pentafluorobenzene with pyrocatechol and its
derivates (Scheme 2, b).
3. Conclusions
After investigation of phenols with polyfluoroarenes, we
further applied this system to the O-polyfluoroarylation of benzyl
alcohols. Unfortunately, the standard conditions were less
suitable for benzyl alcohol substrates. We found that the reaction
temperature of 60 8C and the reaction time for 18 h were
determined to be optimal. As revealed in Table 3, the reaction
conditions were compatible with a number of benzyl alcohols,
including substrates bearing electron-donating and electron-
withdrawing groups and most of the reactants afforded the
polyfluoroaryl benzyl ethers in good to high yields (entries 5a–
5o). To our delight, when the reaction of long-chain aliphatic
alcohols such as pentanol and octanol with 1a was carried out
under the given conditions, the reaction could also proceed, albeit
lower yields were observed (entries 5p–5r). These results again
confirm that this strategy gives highly selective products via C4–F
bond cleavage/C–O bond formation of polyfluorobenzene with
alcohols.
To test the versatility of this methodology, we carried out
several comparative experiments. Reactions of hydroquinone
and benzene-1,3,5-triol with an excess amount of pentafluor-
obenzene smoothly proceeded at all of the hydroxyl groups to
give the corresponding tetrafluoropheny ether compounds 6
and 8, respectively as shown in Scheme 2. Very interestingly,
when hydroquinone was replaced by pyrocatechol, the main
product was cyclic compound 7 rather than di-tetrafluoroaryl
substituted SNAr product. This further proved that our strategy
might be broadened to create polyfluoroary heterocyclic
In summary, we have developed a facile, efficient and transition
metal-free SNAr method for the synthesis of unsymmetrical
polyfluoroaryl ethers via selective C4–F bond cleavage of penta-
fluorobenzene with a wide variety of substituted phenols and
benzyl alcohols. The reaction proceeded smoothly to generate a
series of products in good to excellent yields. Our method is of high
versatility, which is also applicable to other polyfluoroarenes and
long-chain aliphatic alcohols. In addition, this strategy might be
broadened to create polyfluoroary heterocyclic compounds via the
reaction of polyfluorobenzene with pyrocatechol and its derivates.
4. Experimental
1H, 13C, 19F NMR were recorded on Varian Mercury Plus 400
instruments at 400 MHz (1H NMR), 100 MHz (13C NMR), as well as
376 MHz (19F NMR). Chemical shifts were reported in ppm down
field from internal Me4Si and external CCl3F, respectively. Multi-
plicity was indicated as follows: s (singlet), d (doublet), t (triplet), q
(quartet), m (multiplet), dd (doublet of doublet), br (broad).
Coupling constants were reported in Hertz (Hz). Tetrahydrofuran
(THF) and toluene were distilled from sodium/benzophenone;
CH3CN was distilled from P2O5. All purchased reagents were used
without further purification. Analytical thin layer chromatography
was performed on 0.20 mm Qingdao Haiyang silica gel plates. Silica
gel (200–300 mesh) (from Qingdao Haiyang Chem. Company, Ltd.)

56
C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
was used for flash column chromatography. Standard reagents and
solvents were purified according to known procedures.
(100 MHz, CDCl3)
JCÀF = 251 Hz), 133.7 (m), 135.3, 130.6, 124.5, 116.2, 113.8, 102.4 (t,
JC–F = 23 Hz); IR (KBr)
(cmÀ1): 3085, 2927, 2855, 2404, 2353,
d 157.6, 146.5 (dm, JCÀF = 247 Hz), 141.4 (dm,
n
4.1. General procedure for the synthesis of the products (4-
phenylphenol with pentafluorobenzene as the example)
2078, 1642, 1591, 1521, 1432, 1407, 1301, 1273, 1209, 1180, 1129,
1100, 1072, 948, 872, 840, 777, 717, 677.15, 638, 443; MS (EI):
m/z 276.2.
4-Phenylphenol 2 (34.0 mg, 0.2 mmol) and cesium carbonate
(97.7 mg, 0.3 mmol) were weighed to a sealed Schlenk (25 mL)
under Ar atmosphere. Pentafluorobenzene 1a (50.4 mg, 0.3 mmol)
and DMSO (2.0 mL) were added to the sealed Schlenk via syringe at
room temperature respectively. The mixture was stirred at room
temperature until the completion of the reaction (by TLC). Water
(5 mL) was added and the mixture was extracted with ethyl
acetate (3 Â 10 mL). The organic extracts were combined, dried
with anhydrous magnesium sulfate and then concentrated in
vacuo. The residue was purified on silica gel to afford the product
3o (54.1 mg, 85% yield).
4.1.6. 3-(3-Bromophenoxy)-1,2,4,5-tetrafluorobenzene (3f)
55.9 mg, Yield: 87%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
7.29 (d, J = 8.2 Hz, 1H), 7.23 (t, J = 8.1 Hz, 1H), 7.17 (s, 1H), 7.08–
6.98 (m, 1H), 6.95 (d, J = 6.8 Hz, 1H); 19F NMR (376 MHz, CDCl3)
[ppm]
NMR (100 MHz, CDCl3)
d
À138.13–À138.24 (m, 2F), À153.77–À153.88 (m, 2F); 13C
d 157.6, 146.5 (dm, JC–F = 247 Hz), 141.4
(dm, JC–F = 250 Hz), 133.7 (m), 130.9, 127.0, 123.0, 119.1, 114.3,
102.4 (t, JC–F = 22 Hz); IR (KBr)
(cmÀ1): 3084, 2927, 2855, 1642,
n
1585, 1521, 1487, 1428, 1406, 1274, 1203, 1180, 1069, 947, 851,
840, 717, 676, 635, 596, 438.
4.1.1. 1,2,4,5-Tetrafluoro-3-phenoxybenzene (3a)
4.1.7. 1,2,4,5-Tetrafluoro-3-(3-methoxyphenoxy)benzene (3g)
41.7 mg, Yield: 86%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
52.8 mg, Yield: 97%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
7.37 (t, J = 8.0 Hz, 2H), 7.15 (t, J = 7.4 Hz, 1H), 7.05–6.94 (m, 3H); 19F
7.25 (t, J = 8.3 Hz, 1H), 7.05–6.94 (m, 1H), 6.70 (d, J = 8.3 Hz, 1H),
NMR (376 MHz, CDCl3) [ppm]
d
À138.72–À138.73 (m, 2F),
6.64–6.52 (m, 2H), 3.83 (s, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À154.00–À154.10 (m, 2F); 13C NMR (100 MHz, CDCl3) [ppm]
d
À138.74–À138.85 (m, 2F), À154.09–À154.20 (m, 2F); 13C NMR
157.2, 146.5 (dm, JCÀF = 246 Hz), 141.6 (dm, JC–F = 250 Hz), 134.3
(100 MHz, CDCl3) d 161.0, 158.3, 146.5 (dm, JC–F = 247 Hz), 141.6
(m), 129.8, 123.8, 115.6, 101.9 (t, JC–F = 13 Hz); IR (KBr)
n
(cmÀ1): IR
(dm, JC–F = 251 Hz), 134.1 (m), 130.2, 109.1, 107.4, 102.3, 102.0 (t,
JC–F = 23 Hz), 55.4; IR (KBr)
(cmÀ1): 3081, 2947, 2841, 1606, 1521,
(KBr)
n
(cmÀ1): 2957, 2922, 2852, 1710, 1591, 1486, 1466, 1261,
n
1205, 1079, 965, 913, 799, 746; MS (EI): m/z 242.2.
1487, 1263, 1184, 1143, 1068, 947, 838, 762, 712, 647; MS (EI): m/z
272.2.
4.1.2. 1,2,4,5-Tetrafluoro-3-(o-tolyloxy)benzene (3b)
48.2 mg, Yield: 94%; Yellow oil; 1H NMR (400 MHz, CDCl3)
7.29 (d, J = 7.5 Hz, 1H), 7.15 (t, J = 7.5 Hz, 1H), 7.07 (t, J = 7.1 Hz, 1H),
7.03–6.93 (m, 1H), 6.67 (d, J = 8.0 Hz, 1H), 2.47 (s, 3H); 19F NMR
d
4.1.8. 4-(2,3,5,6-Tetrafluorophenoxy)benzonitrile (3i)
40.6 mg, Yield: 76%; Yellow solid; Mp: 98–100 8C; 1H NMR
(400 MHz, CDCl3)
d
7.67 (d, J = 8.7 Hz, 2H), 7.14–7.01 (m, 3H); 19F
(376 MHz, CDCl3) [ppm]
d
À138.94–À139.06 (m, 2F), À154.75–
NMR (376 MHz, CDCl3) [ppm]
d
À137.54–À137.65 (m, 2F),
À154.85 (m, 2F); 13C NMR (100 MHz, CDCl3) [ppm]
d
155.6, 146.5
À153.46–À153.57 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 159.8,
(dm, JC–F = 246 Hz), 141.2 (dm, JC–F = 249 Hz), 134.9 (m), 131.5,
127.3, 126.9, 123.7, 113.5, 101.5 (t, JC–F = 13 Hz), 15.9; IR (KBr)
(cmÀ1): 3083, 2928, 1641, 1588, 1520, 1487, 1274, 1177, 1118,
146.5 (dm, JCÀF = 248 Hz), 141.1 (dm, JCÀF = 252 Hz), 134.4, 132.8
n
(m), 118.2, 116.2, 107.2, 103.1 (t, JC–F = 23 Hz); IR (KBr) n
(cmÀ1):
3062, 2925, 2854, 2230, 1602, 1512, 1488, 1222, 1190, 1067, 946,
1066, 945, 833, 712, 642; MS (EI): m/z 256.2.
868, 836, 544; MS (EI): m/z 267.2.
4.1.3. 3-(2-Bromophenoxy)-1,2,4,5-tetrafluorobenzene (3c)
4.1.9. 3-(4-Bromophenoxy)-1,2,4,5-tetrafluorobenzene (3j)
46.9 mg, Yield: 73%; Yellow solid; Mp: 54–56 8C; 1H NMR
59.7 mg, Yield: 97%; White solid; Mp: 44–46 8C; 1H NMR
(400 MHz, CDCl3)
7.06–6.97 (m, 2H), 6.78 (d, J = 8.2 Hz, 1H); 19F NMR (376 MHz,
CDCl3) [ppm]
À138.36–À138.47 (m, 2F), À153.98–À154.09 (m,
2F); 13C NMR (100 MHz, CDCl3) [ppm]
153.6, 146.5 (dm, JC–
F = 247 Hz), 141.1 (dm, JC–F = 250 Hz), 134.2 (m), 134.1, 128.6,
125.1, 115.5, 112.0, 102.2 (t, JC–F = 22 Hz); IR (KBr)
(cmÀ1): 3084,
d
7.66 (dd, J = 7.9, 1.2 Hz, 1H), 7.28–7.23 (m, 1H),
(400 MHz, CDCl3) d 7.46 (d, J = 8.9 Hz, 2H), 7.07–6.94 (m, 1H), 6.90
(d, J = 8.8 Hz, 2H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À138.26–
d
À138.37 (m, 2F), À153.90–À154.01 (m, 2F); 13C NMR (100 MHz,
d
CDCl3) d 156.2, 146.5 (dm, JC–F = 247 Hz), 141.1 (dm, JC–F = 251 Hz),
133.9 (m), 132.8, 117.4, 116.4, 103.1 (t, JC–F = 23 Hz); IR (KBr)
n
n
(cmÀ1): 3075, 2922, 1888, 1636, 1587, 1516, 1403, 1275, 1216,
1173, 1067, 941, 832, 715, 629, 498.
2927, 2855, 1642, 1578, 1522, 1473, 1443, 1406, 1266, 1219, 1176,
1127, 1071, 1032, 948, 840, 746, 715, 600, 591, 438.
4.1.10. 1,2,4,5-Tetrafluoro-3-(p-tolyloxy)benzene (3k)
4.1.4. 2-(2,3,5,6-Tetrafluorophenoxy)aniline (3d)
46.1 mg, Yield: 90%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
36.5 mg, Yield: 71%; Yellow solid; Mp: 40–42 8C; 1H NMR
7.16 (d, J = 8.1 Hz, 2H), 6.98 (td, J = 9.9, 5.0 Hz, 1H), 6.92 (d,
(400 MHz, CDCl3)
d
6.98 (dd, J = 8.5, 4.3 Hz, 2H), 6.85 (d, J = 7.6 Hz,
J = 8.4 Hz, 2H), 2.36 (s, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
1H), 6.66 (q, J = 7.9 Hz, 2H), 4.01 (s, 2H); 19F NMR (376 MHz, CDCl3)
À138.90–À139.02 (m, 2F), À154.21–À154.32 (m, 2F); 13C NMR
[ppm]
d
À138.72–À138.83 (m, 2F), À154.57–À154.68 (m, 2F); 13C
(100 MHz, CDCl3) d 155.2, 146.5 (dm, JC–F = 247 Hz), 141.6 (dm,
NMR (100 MHz, CDCl3)
d
146.4 (dm, JC–F = 247 Hz), 141.5 (dm, JC–
JC–F = 249 Hz), 134.7 (m), 133.3, 130.2, 115.5, 101.6 (t, JC–
F = 22 Hz), 20.5; IR (KBr)
(cmÀ1): 3084, 2928, 2866, 1641,
F = 249 Hz), 145.0, 136.5, 134.8 (m), 124.6, 118.4, 116.6, 114.3,
101.7 (t, JC–F = 22 Hz); IR (KBr)
(cmÀ1): 3477, 3390, 3076, 2924,
n
n
1608, 1521, 1485, 1203, 1173, 1067, 943, 834, 766, 749, 692, 473;
2854, 1623, 1520, 1305, 1277, 1181, 1073, 945, 839, 743, 714; MS
MS (EI): m/z 256.2.
(EI): m/z 257.2.
4.1.11. 1,2,4,5-Tetrafluoro-3-(4-methoxyphenoxy)benzene (3l)
52.3 mg, Yield: 96%; White solid; Mp: 45–47 8C; 1H NMR
4.1.5. 3-(3-Chlorophenoxy)-1,2,4,5-tetrafluorobenzene (3e)
39.3 mg, Yield: 71%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
(400 MHz, CDCl3) d 7.01–6.90 (m, 3H), 6.87 (d, J = 9.1 Hz, 2H), 3.81
7.29 (t, J = 8.2 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H), 7.08–6.97 (m, 2H),
(s, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À138.95–À139.05 (m,
6.90 (d, J = 9.6 Hz, 1H); 19F NMR (376 MHz, CDCl3) [ppm]
d
2F), À154.47–À154.58 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 156.0,
À138.19–À138.30 (m, 2F), À153.83–À153.94 (m, 2F); 13C NMR
151.3, 146.5 (dm, JC–F = 247 Hz), 141.6 (dm, JC–F = 249 Hz), 135.2

C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
57
(m), 116.9, 114.8, 101.5 (t, JC–F = 23 Hz), 55.6; IR (KBr)
n
(cmÀ1):
NMR (376 MHz, CDCl3) [ppm]
d
À137.45–À137.57 (m, 2F),
3090, 2963, 2842, 1896, 1865, 1834, 1642, 1518, 1485, 1460, 1274,
1248, 1179, 1102, 1066, 1030, 941, 833, 768, 729, 711, 567, 521,
507; MS (EI): m/z 272.2.
À145.01–À145.14 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 160.8,
146.2 (dm, JC–F = 249 Hz), 142.9 (dm, JC–F = 249 Hz), 141.0, 137.3,
122.0, 120.1 (m), 106.9 (t, JC–F = 22 Hz), 106.8; IR (KBr)
n
(cmÀ1):
3415, 3053, 2920, 2852, 1674, 1590, 1515, 1275, 1148, 1074, 945,
4.1.12. 3-(4-Tert-butylphenoxy)-1,2,4,5-tetrafluorobenzene (3m)
56.7 mg, Yield: 97%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
844, 757, 732, 516; MS (EI): m/z 243.2.
7.39 (d, J = 8.8 Hz, 2H), 7.04–6.91 (m, 3H), 1.36 (s, 9H); 19F
4.1.18. 1-(2,3,5,6-Tetrafluorophenoxy)naphthalene (3t)
NMR (376 MHz, CDCl3) [ppm]
d
À138.88–À139.00 (m, 2F),
54.4 mg, Yield: 93%; White solid; Mp: 63–66 8C; 1H NMR
À154.02–À154.13 (m, 2F); 13C NMR (100 MHz, CDCl3)
d
155.0,
(400 MHz, CDCl3)
d 8.49 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 8.6 Hz, 1H),
146.7, 146.5 (dm, JC–F = 247 Hz), 141.7 (dm, JC–F = 245 Hz),
134.6 (m), 126.6, 115.0, 101.7 (t, JC–F = 23 Hz), 34.3, 31.4; IR
7.71–7.58 (m, 3H), 7.37 (t, J = 8.0 Hz, 1H), 7.12–6.98 (m, 1H), 6.75
(d, J = 7.5 Hz, 1H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À138.48–
(KBr)
n
(cmÀ1): 3083, 2965, 2872, 1640, 1606, 1521, 1409,
À138.59 (m, 2F), À153.87–À153.98 (m, 2F); 13C NMR (100 MHz,
1366, 1271, 1212, 1176, 1067, 945, 833, 718, 547; MS (EI):
CDCl3) d 153.2, 147.1 (dm, JC–F = 247 Hz), 141.6 (dm, JC–F = 248 Hz),
m/z 298.9.
134.9, 134.5 (m), 127.7, 127.0, 126.3, 125.2, 124.9, 123.6, 121.7,
107.7, 102.1 (t, JC–F = 23 Hz); IR (KBr)
(cmÀ1): 3092, 2923, 1627,
n
4.1.13. 4-(2,3,5,6-Tetrafluorophenoxy)aniline (3n)
1599, 1518, 1463, 1245, 1210, 1163, 1119, 1060, 942, 817, 750,
725, 475; MS (EI): m/z 292.3.
38.6 mg, Yield: 75%; Yellow solid; Mp: 48–50 8C; 1H NMR
(400 MHz, CDCl3)
d 6.93 (ddd, J = 19.9, 10.0, 7.1 Hz, 1H), 6.86 (d,
J = 8.7 Hz, 2H), 6.64 (d, J = 8.8 Hz, 2H), 3.53 (s, 2H); 19F NMR
4.1.19. 2-(2,3,5,6-Tetrafluorophenoxy)naphthalene (3u)
(376 MHz, CDCl3) [ppm]
d
À139.15–À139.27 (m, 2F), À154.63–
53.2 mg, Yield: 91%; White solid; Mp: 89–93 8C; 1H NMR
À154.74 (m, 2F); 13C NMR (100 MHz, CDCl3)
d
150.2, 146.3 (dm, JC–
(400 MHz, CDCl3)
d 7.89 (t, J = 8.5 Hz, 2H), 7.76 (d, J = 8.0 Hz, 1H),
F = 246 Hz), 142.8, 141.6 (dm, JC–F = 249 Hz), 135.5 (m), 117.1,
116.0, 101.2 (t, JC–F = 23 Hz); IR (KBr)
3081, 2924, 1640, 1518, 1485, 1271, 1198, 1125, 1067, 945, 830,
714, 515; MS (EI): m/z 257.2.
7.51 (dt, J = 14.8, 7.0 Hz, 2H), 7.39 (d, J = 8.9 Hz, 1H), 7.26 (s, 1H),
n
(cmÀ1): 3455, 3375, 3222,
7.11–6.96 (m, 1H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À138.48–
À138.59 (m, 2F), À153.87–À153.98 (m, 2F); 13C NMR (100 MHz,
CDCl3) d 155.1, 146.6 (dm, JCÀF = 247 Hz), 141.7 (dm, JC–
F = 251 Hz), 134.3 (m), 134.0, 130.4, 130.3, 127.9, 127.2, 127.0,
4.1.14. 4-(2,3,5,6-Tetrafluorophenoxy)biphenyl (3o)
125.1, 117.2, 110.3, 102.1 (t, JC–F = 23 Hz); IR (KBr)
n
(cmÀ1):
54.1 mg, Yield: 85%; White solid; Mp: 129–133 8C; 1H NMR
3077, 2925, 2854, 1641, 1599, 1577, 1520, 1445, 1392, 1259,
1228, 1176, 1128, 1099, 1068, 945, 838, 770, 719, 650, 562;
MS (EI): m/z 292.3.
(400 MHz, CDCl3)
d 7.61 (d, J = 8.4 Hz, 4H), 7.49 (t, J = 7.5 Hz, 2H),
7.40 (t, J = 7.3 Hz, 1H), 7.11 (d, J = 8.5 Hz, 2H), 7.03 (ddd, J = 16.9,
9.8, 7.1 Hz, 1H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À138.50–
À138.62 (m, 2F), À153.84–À153.95 (m, 2F); 13C NMR (100 MHz,
4.1.20. 4-(2,3,5,6-Tetrafluoro-4-(trifluoromethyl)phenoxy)biphenyl
(4a)
CDCl3)
d 156.7, 146.5 (dm, JC–F = 247 Hz), 141.6 (dm, JC–
F = 251 Hz), 140.2, 137.1, 135.5 (m), 128.8, 128.6, 127.3, 127.0,
115.9, 102.0 (t, JC–F = 22 Hz); IR (KBr)
(cmÀ1): 3091, 2923, 2853,
62.6 mg, Yield: 81%; White solid; Mp: 130–134 8C; 1H NMR
n
(400 MHz, CDCl3)
d 7.61 (t, J = 8.7 Hz, 4H), 7.48 (t, J = 7.3 Hz, 2H),
1641, 1598, 1517, 1490, 1405, 1225, 1176, 1119, 1067, 943, 834,
766, 749, 692, 473.
7.40 (t, J = 6.9 Hz, 1H), 7.12 (d, J = 8.2 Hz, 2H); 19F NMR (376 MHz,
CDCl3) [ppm]
d
À55.8–À56.1 (m, 3F), À140.28–À140.48 (m, 2F),
À151.82–À152.04 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 156.1,
4.1.15. 3-(2,3-Dimethylphenoxy)-1,2,4,5-tetrafluorobenzene (3p)
50.8 mg, Yield: 94%; Yellow solid; Mp: 89–91 8C; 1H NMR
145.0 (dm, JC–F = 256 Hz), 141.8 (dm, JC–F = 252 Hz), 140.0, 137.9,
137.5 (m), 128.9, 128.6, 127.4, 127.0, 120.9 (q, JC–F = 252 Hz),
116.3, 105.8 (m); IR (KBr) n
(cmÀ1): 3077, 2924, 2854, 1620,
1
(400 MHz, CDCl3)
d
7.04 (t, J = 7.8 Hz, 1H), 7.01–6.91 (m, 2H), 6.54
(d, J = 8.0 Hz, 1H), 2.39 (s, 6H); 19F NMR (376 MHz, CDCl3) [ppm]
d
1599, 1453, 1429, 1303, 1246, 1224, 1138, 1097, 871, 833,
758, 689.
À138.50–À138.62 (m, 2F), À139.05–À139.16 (m, 2F); 13C NMR
(100 MHz, CDCl3)
d 155.5, 146.0 (dm, JC–F = 246 Hz), 141.5 (dm, JC–
F = 248 Hz), 139.0, 135.2 (m), 126.0, 125.8, 125.3, 111.2, 101.3 (t, JC–
F = 22 Hz), 20.0, 11.8; IR (KBr)
(cmÀ1): 3093, 2923, 2527, 1643,
4.1.21. 4-(Perfluorophenoxy)biphenyl (4b)
n
34.3 mg, Yield: 51%; White solid; Mp: 130–132 8C; 1H NMR
1609, 1581, 1516, 1492, 1234, 1177, 1163, 1126, 1110, 939, 846,
763, 641; MS (EI): m/z 270.3.
(400 MHz, CDCl3)
d 7.60 (d, J = 7.7 Hz, 4H), 7.49 (t, J = 7.4 Hz, 2H),
7.40 (t, J = 7.2 Hz, 1H), 7.08 (d, J = 8.3 Hz, 2H); 19F NMR (376 MHz,
CDCl3) [ppm]
d
À153.82–À153.86 (m, F), À159.73–À159.85 (m,
4.1.16. 3-(3,4-Dimethylphenoxy)-1,2,4,5-tetrafluorobenzene (3q)
2F), À161.91–À162.04 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 156.7,
49.2 mg, Yield: 91%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
142.2 (dm, JC–F = 247 Hz), 140.2, 138.3 (dm, JC–F = 257 Hz), 137.7
(m), 137.3, 129.8 (m), 128.8, 128.7, 127.3, 127.0, 115.8, 112.3 (t, JC–
F = 20 Hz); IR (KBr)
7.12 (d, J = 8.2 Hz, 1H), 7.05–6.92 (m, 1H), 6.85 (s, 1H), 6.75 (d,
J = 6.9 Hz, 1H), 2.29 (d, J = 7.7 Hz, 6H); 19F NMR (376 MHz,
n
(cmÀ1): 1517, 1225, 1172, 1115, 998, 835,
CDCl3) [ppm]
(m, 2F); 13C NMR (100 MHz, CDCl3)
F = 246 Hz), 141.7 (dm, JC–F = 247 Hz), 138.4, 134.8 (m), 132.0,
d
À138.98–À139.09 (m, 2F), À139.05–À139.16
765, 693.
d
155.4, 146.5 (dm, JC–
4.1.22. 4-(2,3,5,6-Tetrafluoro-4-methylphenoxy)biphenyl (4c)
55.2 mg, Yield: 83%; White solid; Mp: 131–134 8C; 1H NMR
(400 MHz, CDCl3)
130.6, 116.9, 112.6, 101.6 (t, JC–F = 22 Hz), 19.9, 18.9; IR (KBr)
n
(cmÀ1): 3084, 3028, 2926, 1641, 1612, 1520, 1485, 1275, 1242,
1196, 1177, 1155, 1116, 1069, 947, 808, 713, 638, 443; MS (EI):
m/z 270.3.
d 7.59 (d, J = 7.8 Hz, 4H), 7.48 (t, J = 7.5 Hz, 2H),
7.38 (t, J = 7.3 Hz, 1H), 7.09 (d, J = 8.4 Hz, 2H), 2.33 (d, J = 16.8 Hz,
3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À143.43–À143.52 (m, 2F),
À155.65–À155.74 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 156.9,
4.1.17. 2-(2,3,5,6-Tetrafluorophenoxy)pyridine (3s)
145.5 (dm, JC–F = 245 Hz), 141.5 (dm, JC–F = 250 Hz), 140.3, 131.2
(m), 136.8, 128.8, 128.5, 127.2, 127.0, 115.8, 112.3 (t, JC–F = 20 Hz),
25.8 mg, Yield: 53%; Yellow solid; Mp: 154–158 8C; 1H NMR
(400 MHz, CDCl3)
d
7.47 (t, J = 8.0 Hz, 1H), 7.30–7.20 (m, 1H), 7.18
7.2; IR (KBr)
962, 929, 835, 759, 691, 478.
n
(cmÀ1): 1654, 1598, 1493, 1229, 1198, 1115, 1065,
(d, J = 7.0 Hz, 1H), 6.71 (d, J = 9.4 Hz, 1H), 6.33 (t, J = 6.7 Hz, 1H); 19F

58
C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
4.1.23. 4-(3,4-Difluorophenoxy)biphenyl (4d)
4.1.29. 3-(4-Bromobenzyloxy)-1,2,4,5-tetrafluorobenzene (5f)
54.3 mg, Yield: 81%; Yellow oil; 1H NMR (400 MHz, CDCl3)
40.1 mg, Yield: 71%; White solid; Mp: 63–65 8C; 1H NMR
d
(400 MHz, CDCl3)
d
7.67–7.58 (m, 4H), 7.49 (t, J = 7.6 Hz, 2H), 7.40 (t,
7.53 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H), 6.86–6.73 (m, 1H),
J = 7.3 Hz, 1H), 7.24–7.09 (m, 3H), 6.90–6.80 (m, 2H); 19F NMR
5.22 (s, 2H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À139.71–À139.83
(376 MHz, CDCl3) [ppm]
d
À115.91–À116.00 (m, F), À136.74–
(m, 2F), À156.06–À156.17 (m, 2F); 13C NMR (100 MHz, CDCl3)
d
À136.83 (m, F); 13C NMR (100 MHz, CDCl3)
d
156.0, 140.4, 137.2,
146.3 (dm, JC–F = 246 Hz), 141.3 (dm, JC–F = 250 Hz), 137.3 (m),
134.6, 131.8, 129.8, 123.0, 100.0 (t, JC–F = 23 Hz), 75.5 (t, JC–
F = 3 Hz), 55.2; IR (KBr) n
(cmÀ1): 3085, 2967, 2876, 1642, 1596,
128.9, 128.6, 127.3, 127.0, 118.3; IR (KBr)
n
(cmÀ1): 3431, 3076,
2924, 2854, 1620, 1599, 1503, 1429, 1303, 1246, 1194, 1097, 967,
871, 833, 758, 689, 482; MS (EI): m/z 282.4.
1516, 1404, 1373, 1267, 1170, 1089, 984, 930, 806, 710, 482.
4.1.24. 3-(Benzyloxy)-1,2,4,5-tetrafluorobenzene (5a)
4.1.30. 1,2,4,5-Tetrafluoro-3-(3-methoxybenzyloxy)benzene (5g)
46.4 mg, Yield: 81%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
40.0 mg, Yield: 78%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
7.47 (d, J = 6.8 Hz, 2H), 7.45–7.38 (m, 3H), 6.85–6.72 (m, 1H), 5.29
7.30 (dd, J = 13.9, 5.8 Hz, 1H), 7.02 (d, J = 6.9 Hz, 2H), 6.92 (d,
J = 7.4 Hz, 1H), 6.85–6.71 (m, 1H), 5.26 (s, 2H), 3.85 (s, 3H); 19F
(s, 2H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À139.98–À140.09 (m,
2F), À155.98–À156.09 (m, 2F); 13C NMR (100 MHz, CDCl3)
d
146.3
NMR (376 MHz, CDCl3) [ppm]
d
À139.94–À140.06 (m, 2F),
(dm, JC–F = 246 Hz), 141.4 (dm, JC–F = 246 Hz), 137.6 (m), 135.6,
128.8, 128.6, 128.3, 99.8 (t, JC–F = 23 Hz), 76.4 (t, JC–F = 3 Hz); IR
À155.96–À156.07 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 159.8,
146.3 (dm, JC–F = 245 Hz), 141.3 (dm, JC–F = 246 Hz), 137.5 (m),
137.1, 129.7, 120.4, 114.6, 113.4, 99.8 (t, JC–F = 23 Hz), 76.2 (t, JC–
(KBr)
n
(cmÀ1): 3082, 3036, 2958, 1641, 1516, 1486, 1377, 1174,
1089, 941, 697, 647; MS (EI): m/z 256.2.
F = 3 Hz), 55.2; IR (KBr) n
(cmÀ1): 3079, 2959, 2840, 1641, 1604,
1516, 1483, 1374, 1269, 1173, 1088, 1051, 940, 766, 693; MS (EI):
4.1.25. 1,2,4,5-Tetrafluoro-3-(2-methoxybenzyloxy)benzene (5b)
51.0 mg, Yield: 89%; White solid; Mp: 36–38 8C; 1H NMR
m/z 286.4.
(400 MHz, CDCl3)
1H), 7.00 (t, J = 7.4 Hz, 1H), 6.93 (d, J = 8.2 Hz, 1H), 6.84–6.72
(m, 1H), 5.35 (s, 2H), 3.86 (s, 3H); 19F NMR (376 MHz, CDCl3)
d
7.45 (d, J = 7.3 Hz, 1H), 7.37 (t, J = 7.6 Hz,
4.1.31. 1,2,4,5-Tetrafluoro-3-(3-phenoxybenzyloxy)benzene (5h)
63.4 mg, Yield: 91%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
7.47–7.32 (m, 3H), 7.27–7.11 (m, 3H), 7.06 (d, J = 7.9 Hz, 3H), 6.87–
[ppm]
d
À140.42–À140.54 (m, 2F), À156.06–À156.17 (m, 2F);
157.7, 146.3 (dm, JC–F = 245 Hz),
6.73 (m, 1H), 5.27 (s, 2H); 19F NMR (376 MHz, CDCl3) [ppm]
d
13C NMR (100 MHz, CDCl3)
d
À139.78–À139.89 (m, 2F), À155.83–À155.94 (m, 2F); 13C NMR
142.5 (dm, JC–F = 246 Hz), 138.2 (m), 130.2, 130.1, 124.2,
120.5, 110.5, 99.5 (t, JC–F = 23 Hz), 72.0 (t, JC–F = 3 Hz), 55.3; IR
(100 MHz, CDCl3) d 157.7, 156.9, 146.3 (dm, JC–F = 246 Hz), 140.3
(dm, JC–F = 246 Hz), 137.5, 137.4 (m), 130.1, 123.6, 122.9, 119.2,
(KBr)
n
(cmÀ1): 3083, 2945, 2841, 1640, 1602, 1515, 1463,
119.1, 118.4, 99.9 (t, JC–F = 23 Hz), 75.9 (t, JC–F = 3 Hz); IR (KBr) n
1376, 1289, 1246, 1172, 1090, 1027, 934, 823, 751, 731; MS
(EI): m/z 286.4.
(cmÀ1): 3079, 2958, 2926, 1641, 1587, 1516, 1487, 1444, 1374,
1253, 1215, 1172, 1089, 944, 829, 693.
4.1.26. 3-(2-Chlorobenzyloxy)-1,2,4,5-tetrafluorobenzene (5c)
4.1.32. 1-((2,3,5,6-Tetrafluorophenoxy)methyl)naphthalene (5i)
50.8 mg, Yield: 83%; White solid; Mp: 37–39 8C; 1H NMR
45.9 mg, Yield: 79%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
7.66–7.57 (m, 1H), 7.47–7.39 (m, 1H), 7.38–7.29 (m, 2H), 6.89–6.75
(400 MHz, CDCl3)
d 8.33 (d, J = 8.3 Hz, 1H), 7.94 (t, J = 7.6 Hz, 2H),
(m, 1H), 5.40 (s, 2H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À139.76–
7.68 (t, J = 7.2 Hz, 1H), 7.61 (t, J = 7.0 Hz, 2H), 7.50 (t, J = 7.6 Hz, 1H),
À139.88 (m, 2F), À156.00–À156.11 (m, 2F); 13C NMR (100 MHz,
6.87–6.69 (m, 1H), 5.75 (s, 2H); 19F NMR (376 MHz, CDCl3) [ppm]
d
CDCl3)
d
146.4 (dm, JC–F = 246 Hz), 141.3 (dm, JC–F = 248 Hz), 137.7
À139.79–À139.91 (m, 2F), À155.54–À155.65 (m, 2F); 13C NMR
(m), 133.5, 133.6, 129.9, 129.8, 129.6, 127.0, 100.0 (t, JC–F = 23 Hz),
73.5 (t, JC–F = 4 Hz), 55.3; IR (KBr)
(cmÀ1): 3084, 2959, 2928, 1641,
(100 MHz, CDCl3) d 146.4 (dm, JC–F = 245 Hz), 141.5 (dm, JC–
n
F = 245 Hz), 137.5 (m), 133.8, 131.8, 131.2, 130.0, 128.7, 127.8,
126.8, 126.2, 125.1, 123.8, 99.9 (t, JC–F = 23 Hz), 74.8 (t, JC–F = 3 Hz);
IR (KBr) n
(cmÀ1): 3616, 3122, 2925, 2853, 2314, 1642, 1515, 1486,
1521, 1448, 1377, 1274, 1213, 1174, 1089, 1055, 941, 831, 755,
714, 568, 438; MS (EI): m/z 290.6.
1401, 1386, 1261, 1173, 1083, 946, 798, 714.
4.1.27. 1,2,4,5-Tetrafluoro-3-(4-methoxybenzyloxy)benzene (5d)
48.7 mg, Yield: 85%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
4.1.33. 1,2,4,5-Tetrafluoro-3-(1-phenylethoxy)benzene (5j)
38.4 mg, Yield: 71%; Yellow oil; 1H NMR (400 MHz, CDCl3)
7.43 (d, J = 7.1 Hz, 2H), 7.40–7.31 (m, 3H), 6.78–6.65 (m, 1H), 5.52
(q, J = 6.4 Hz, 1H), 1.74 (d, J = 6.4 Hz, 3H); 19F NMR (376 MHz,
7.38 (d, J = 8.5 Hz, 2H), 6.92 (d, J = 8.6 Hz, 2H), 6.83–6.70 (m, 1H),
d
5.21 (s, 2H), 3.83 (s, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À140.14–À140.22 (m, 2F), À155.87–À155.98 (m, 2F); 13C NMR
(100 MHz, CDCl3)
d
160.1, 146.3 (dm, JC–F = 246 Hz), 141.5 (dm, JC–
CDCl3) [ppm]
2F); 13C NMR (100 MHz, CDCl3)
(dm, JC–F = 253 Hz), 140.9, 136.8 (m), 128.5, 126.3, 126.2, 99.6 (t, JC–
F = 23 Hz), 82.6 (t, JC–F = 3 Hz), 23.1; IR (KBr)
(cmÀ1): 3080, 2985,
d
À140.25–À140.37 (m, 2F), À155.17–À155.28 (m,
F = 246 Hz), 137.5 (m), 130.2, 127.7, 114.0, 99.7 (t, JC–F = 23 Hz),
76.1 (t, JC–F = 3 Hz), 55.2; IR (KBr)
(cmÀ1): 3079, 2964, 2841, 1641,
d
144.7 (dm, JC–F = 248 Hz), 141.6
n
1587, 1486, 1432, 1402, 1375, 1303, 1253, 1175, 1085, 1035, 944,
n
824, 688; MS (EI): m/z 286.4.
2932, 2858, 1640, 1515, 1482, 1173, 1085, 943, 829, 761, 700, 540;
MS (EI): m/z 270.2.
4.1.28. 3-(4-Chlorobenzyloxy)-1,2,4,5-tetrafluorobenzene (5e)
48.2 mg, Yield: 83%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
4.1.34. 1,2,4,5-Tetrafluoro-3-(1-(3-methoxyphenyl)ethoxy)benzene
7.45–7.32 (m, 4H), 6.86–6.73 (m, 1H), 5.24 (s, 2H); 19F NMR
(5k)
(376 MHz, CDCl3) [ppm]
d
À139.71–À139.83 (m, 2F), À156.06–
45.0 mg, Yield: 75%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
À156.17 (m, 2F); 13C NMR (100 MHz, CDCl3)
d
146.3 (dm, JC–
7.27 (t, J = 7.8 Hz, 1H), 7.06–6.94 (m, 2H), 6.86 (dd, J = 8.2, 1.6 Hz,
1H), 6.79–6.64 (m, 1H), 5.51 (q, J = 6.3 Hz, 1H), 3.84 (s, 3H), 1.73 (d,
F = 246 Hz), 141.3 (dm, JC–F = 250 Hz), 137.3 (m), 134.8, 134.1,
129.6, 128.9, 99.8 (t, JC–F = 23 Hz), 75.4 (t, JC–F = 4 Hz), 55.2; IR
J = 6.4 Hz, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À140.22–
(KBr)
n
(cmÀ1): 3086, 2972, 2877, 1904, 1644, 1604, 1515,
À140.33 (m, 2F), À155.15–À155.26 (m, 2F); 13C NMR (100 MHz,
1406, 1376, 1266, 1170, 1089, 983, 930, 811, 711; MS (EI):
CDCl3) d 159.8, 146.2 (dm, JC–F = 245 Hz), 142.5, 141.5 (dm, JC–
m/z 290.6.
F = 245 Hz), 136.8 (m), 129.6, 118.6, 114.2, 111.5, 99.7 (t, JC–
F = 23 Hz), 82.4 (t, JC–F = 3 Hz), 55.2, 23.2; IR (KBr)
(cmÀ1): 3078,
n

C. Liu et al. / Journal of Fluorine Chemistry 156 (2013) 51–60
59
2985, 2840, 1640, 1605, 1515, 1484, 1376, 1263, 1173, 1122, 1085,
1047, 943, 831, 786, 699.
1.47 (dd, J = 14.1, 6.5 Hz, 2H), 1.37–1.29 (m, 8H), 0.91 (t,
J = 6.2 Hz, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À140.29–
À140.41 (m, 2F), À157.14–À157.24 (m, 2F); 13C NMR
4.1.35. 1,2,4,5-Tetrafluoro-3-(1-(4-methoxyphenyl)ethoxy)benzene
(100 MHz, CDCl3) d 146.3 (dm, JC–F = 245 Hz), 141.2 (dm, JC–
(5l)
F = 245 Hz), 138.3 (m), 99.1 (t, JC–F = 23 Hz), 75.3 (t, JC–F = 3 Hz),
31.7, 29.9, 29.2, 25.5, 22.6, 14.0; IR (KBr)
(cmÀ1): 3083, 2929,
41.4 mg, Yield: 69%;Yellow oil; 1HNMR (400 MHz, CDCl3)
d
7.34
n
(d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.6 Hz, 2H), 6.77–6.64 (m, 1H), 5.48 (q,
J = 6.3 Hz, 1H), 3.81 (s, 3H), 1.72 (d, J = 6.4 Hz, 3H); 19F NMR
2858, 1641, 1516, 1490, 1470, 1385, 1173, 1094, 941, 827, 742,
713; MS (EI): m/z 278.5.
(376 MHz, CDCl3) [ppm]
d
À140.39–À140.51 (m, 2F), À155.13–
À155.24 (m, 2F); 13C NMR (100 MHz, CDCl3)
d
159.8, 146.2 (dm, JC–
4.1.41. 3-(Cyclohexyloxy)-1,2,4,5-tetrafluorobenzene (5r)
F = 246 Hz), 141.6 (dm, JC–F = 250 Hz), 136.9 (m), 132.8, 127.9, 113.9,
99.6(t, JC–F = 23 Hz), 82.2(t, JC–F = 3 Hz), 55.2, 22.9;IR(KBr)
34.8 mg, Yield: 70%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
n
(cmÀ1):
6.87–6.67 (m, 1H), 4.34–4.22 (m, 1H), 2.02–1.95 (m, 2H), 1.84 (dd,
J = 9.4, 5.3 Hz, 2H), 1.65–1.56 (m, 3H), 1.35 (t, J = 8.0 Hz, 3H); 19F
3078, 2985, 2840, 1640, 1605, 1515, 1484, 1376, 1263, 1173, 1122,
1085, 1047, 943, 831,786, 699.
NMR (376 MHz, CDCl3) [ppm]
d
À140.41–À140.52 (m, 2F),
À155.90–À156.00 (m, 2F); 13C NMR (100 MHz, CDCl3)
d 146.3
4.1.36. 3-(1-(4-Chlorophenyl)ethoxy)-1,2,4,5-tetrafluorobenzene
(dm, JC–F = 252 Hz), 141.8 (dm, JC–F = 245 Hz), 137.1 (m), 99.3 (t, JC–
F = 23 Hz), 83.1, 32.3, 25.3, 23.5; IR (KBr) n
(cmÀ1): 2937, 2860,
(5m)
44.5 mg, Yield: 73%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
1653, 1482, 1372, 1260, 1176, 1126, 992, 935, 708; MS (EI):
7.35 (q, J = 8.6 Hz, 4H), 6.80–6.67 (m, 1H), 5.48 (q, J = 6.4 Hz, 1H),
m/z 248.2.
1.71 (d, J = 6.4 Hz, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À139.93–À140.04 (m, 2F), À155.23–À155.34 (m, 2F); 13C NMR
4.1.42. 1,4-Bis(2,3,5,6-tetrafluorophenoxy)benzene (6)
(100 MHz, CDCl3)
d
146.2 (dm, JC–F = 246 Hz), 141.4 (dm, JC–
56.1 mg, Yield: 69%; White solid; Mp: 130–133 8C;1H NMR
F = 246 Hz), 139.4, 136.6 (m), 134.4, 128.8, 127.7, 99.9 (t, JC–
F = 23 Hz), 81.8 (t, JC–F = 3 Hz), 23.1; IR (KBr)
(cmÀ1): 3085, 2986,
(400 MHz, CDCl3) d
7.05–6.92 (m, 6H); 19F NMR (376 MHz, CDCl3)
n
[ppm]
d
À138.50–À138.61 (m, 4F), À154.07–À154.18 (m, 4F); 13C
2855, 1640, 1516, 1484, 1410, 1377, 1342, 1270, 1173, 1084, 996,
788, 714, 539.
NMR (100 MHz, CDCl3) d 153.3, 146.5 (dm, JC–F = 247 Hz), 141.5
(dm, JC–F = 249 Hz), 134.6 (m), 117.0, 102.0 (t, JC–F = 22 Hz); IR
(KBr)
(cmÀ1): 2921, 1622, 1519, 1276, 1175, 941, 834, 685,
n
4.1.37. 3-(1-(4-Bromophenyl)ethoxy)-1,2,4,5-tetrafluorobenzene
(5n)
630, 508.
48.9 mg, Yield: 70%; Yellow oil; 1H NMR (400 MHz, CDCl3)
4.1.43. 1,2,4-Trifluorodibenzo[b,e][1,4]dioxine (7)
d
7.49 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.3 Hz, 2H), 6.80–6.66 (m,
33.8 mg, Yield: 71%; White solid; Mp: 137–140 8C;1H NMR
1H), 5.47 (q, J = 6.4 Hz, 1H), 1.70 (d, J = 6.4 Hz, 3H); 19F NMR
(400 MHz, CDCl3)
d 7.03–6.95 (m, 4H), 6.65 (td, J = 10.1, 6.8 Hz,
(376 MHz, CDCl3) [ppm]
d
À139.88–À140.00 (m, 2F),
1H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À138.65–À138.81 (m,
À155.22–À155.33 (m, 2F); 13C NMR (100 MHz, CDCl3)
d
F), À140.50–À140.59 (m, F), À162.95–À163.06 (m, F); 13C NMR
146.2 (dm, JC–F = 246 Hz), 141.4 (dm, JC–F = 246 Hz), 140.0,
136.6 (m), 131.8, 128.0 122.5, 99.9 (t, JC–F = 23 Hz), 81.8 (t, JC–
(100 MHz, CDCl3) d 140.6, 140.2, 125.2, 124.9, 124.7, 116.9; IR
(KBr)
n
(cmÀ1): 3439, 3128, 2924, 2852, 2313, 1731, 1644,
F = 3 Hz), 23.1; IR (KBr)
n
(cmÀ1): 3084, 2986, 2932, 1641,
1522, 1489, 1401, 1257, 1175, 1137, 1070, 946; MS (EI):
1516, 1484, 1407, 1377, 1341, 1298, 1209, 1123, 1083, 1010,
945, 780, 714, 536.
m/z 238.3.
4.1.44. 1,3,5-Tris(2,3,5,6-tetrafluorophenoxy)benzene (8)
4.1.38. (2,3,5,6-Tetrafluorophenoxy)methylene)dibenzene (5o)
56.5 mg, Yield: 89%; White solid; Mp: 56–59 8C; 1H NMR
60.4 mg, Yield: 53%; White solid; Mp: 67–70 8C;1H NMR
(400 MHz, CDCl3)
d
7.09–6.98 (m, 3H), 6.36 (s, 3H); 19F NMR
(400 MHz, CDCl3)
d
7.54 (d, J = 7.1 Hz, 4H), 7.45–7.35 (m, 6H), 6.79–
(376 MHz, CDCl3) [ppm]
d
À137.81–À137.94 (m, 6F), À153.37–
6.66 (m, 1H), 6.57 (s, 1H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À153.48 (m, 6F); 13C NMR (100 MHz, CDCl3)
d 158.8, 146.4 (dm, JC–
À139.99–À140.11 (m, 2F), À155.35–À155.45 (m, 2F); 13C NMR
F = 248 Hz), 141.3 (dm, JC–F = 252 Hz), 133.1 (m), 102.8 (t, JC–
F = 22 Hz), 98.9; IR (KBr) n
(cmÀ1): 3091, 2962, 2855, 1611, 1524,
(100 MHz, CDCl3)
d
146.3 (dm, JC–F = 245 Hz), 141.5 (dm, JC–
F = 245 Hz), 139.8, 136.6 (m), 128.7, 128.5, 127.2, 99.9 (t, JC–
F = 24 Hz), 86.8; IR (KBr)
(cmÀ1): 3077, 3034, 2959, 1955, 1640,
1486, 1464, 1274, 1179, 1139, 1073, 944, 840, 716.
n
1515, 1481, 1454, 1399, 1349, 1226, 1172, 1118, 1108, 974, 935,
931, 700, 593.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (No 11074185) and Innovation
Foundation of Tianjin University. We acknowledge Prof. Jun-An
Ma for helpful discussion.
4.1.39. 1,2,4,5-Tetrafluoro-3-(pentyloxy)benzene (5p)
29.8 mg, Yield: 63%; Yellow oil; 1H NMR (400 MHz, CDCl3)
d
6.77 (tt, J = 10.0, 7.0 Hz, 1H), 4.24 (t, J = 6.6 Hz, 2H), 1.85–
1.76 (m, 2H), 1.43 (ddd, J = 21.2, 13.5, 6.3 Hz, 4H), 0.95 (t,
J = 7.1 Hz, 3H); 19F NMR (376 MHz, CDCl3) [ppm]
d
À140.26–
À140.37 (m, 2F), À157.13–À157.23 (m, 2F); 13C NMR
Appendix A. Supplementary data
(100 MHz, CDCl3)
d 145.4 (dm, JC–F = 246 Hz), 141.2 (dm, JC–
F = 245 Hz), 138.4 (m), 99.1 (t, JC–F = 23 Hz), 75.3 (t, JC–F = 4 Hz),
29.6, 27.7, 22.3, 13.9; IR (KBr)
(cmÀ1): 3480, 3346, 3074,
2959, 2855, 1654, 1487, 1372, 1261, 1125, 1085, 997, 936,
Supplementary material related to this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jfluchem.2013.
08.013.
n
800, 707; MS (EI): m/z 236.6.
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