Synthesis of perfluorinated biaryls by reaction of perfluoroarylzinc compounds with perfluoroarenes

Article abstract of DOI:10.1134/S107042801510005X

Symmetrical and unsymmetrical perfluorinated biaryls have been synthesized by reactions of perfluorinated benzonitrile, nitrobenzene, toluene, m-xylene, and pyridine with perfluoroarylzinc compounds derived from chloropentafluorobenzene, octafluorotoluene

Full text of DOI:10.1134/S107042801510005X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 10, pp. 1388–1394. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.S. Vinogradov, V.E. Platonov, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 10, pp. 1419–1425.
Synthesis of Perfluorinated Biaryls by Reaction
of Perfluoroarylzinc Compounds with Perfluoroarenes
A. S. Vinogradov and V. E. Platonov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: platonov@nioch.nsc.ru
Received February 18, 2015
Abstract—Symmetrical and unsymmetrical perfluorinated biaryls have been synthesized by reactions of
perfluorinated benzonitrile, nitrobenzene, toluene, m-xylene, and pyridine with perfluoroarylzinc compounds
derived from chloropentafluorobenzene, octafluorotoluene, and pentafluoropyridine. The described transforma-
tions may be regarded as nucleophilic aromatic substitution.
DOI: 10.1134/S107042801510005X
Since the discovery of cross-coupling reactions,
considerable attention has been given to the synthesis
of polyfluoroinated biaryls [1–4]. These compounds
are used in medicinal chemistry [5] and in the prepara-
tion of organic semiconductors [6], organic light-
emitting diodes (OLEDs) [7], liquid crystals [8],
metal–organic frameworks (MOFs) [9], polymers of
intrinsic microporosity (PIMs) [10], and organic mole-
cules of intrinsic microporosity (OMIMs) [11]. Poly-
fluorinated biaryls are generally synthesized by
cross-coupling of polyfluoroarenes with aryl halides
(Hlg = I, Br, Cl) in the presence of a palladium catalyst
and a base [12, 13], as well as with arylboronic acids
in the presence of a palladium catalyst and an oxidant
[14]. Di-, tri-, and tetrafluorophenylboronic acids react
with aryl halides in the presence of a palladium cata-
lyst to give polyfluorinated biaryls [15–22]. Penta-
fluorophenylboronic acid is inactive in Suzuki reac-
tions, and only the use of a more complex palladium
catalyst containing Ag2O and CsF additives ensured
formation of polyfluorobiaryls in high yields in reac-
tions with aromatic iodides and bromides [23]. How-
ever, the yield of pentafluorobiphenyl in the reaction
with chlorobenzene was as low as 39% [23]. Cross-
coupling of polyfluorophenylboronic acid lithium and
potassium salts with aryl iodides, catalyzed by
Pd/Ag2O gave polyfluorobiphenyls [24–26]. Syntheses
of polyfluorobiphenyls by palladium-catalyzed reac-
tions of bromopolyfluoroarenes with arylboronic acids
were also reported [27–31].
strongest among Carom–Hlg bonds) require search for
efficient catalysts. Nickel-based catalytic systems used
for Kumada reactions with monofluoroarenes turned
out to be ineffective in the arylation of polyfluorinated
aromatics such as hexafluorobenzene. A catalytic
Ni complex stabilized by an N-heterocyclic carbene
(NHC) ensured successful Suzuki arylation of hexa-
fluorobenzene and octafluorotoluene with 4-substituted
phenylboronic acids [32]. Negishi reactions of poly-
fluoroarylzinc reagents (generated in situ) with bromo-
and iodoarenes in the presence of a palladium catalyst
afforded polyfluorobiphenyls [33–35]. The required
organozinc compounds were prepared from poly-
fluoroarenes, BuLi, and ZnCl2 [33] or from polyfluoro-
arylaluminum derivatives which were subjected to
transmetalation with ZnCl2 [35]. The nickel complex
Ni(PCy3)2Cl2 was used to catalyze cross-coupling of
activated and deactivated aryl fluorides with arylzinc
reagents. These reactions were mainly used to synthe-
size non-fluorinated biphenyls [36], and they involved
nickel-catalyzed replacement of fluorine in fluoro-
arenes by an aryl group.
A general procedure for copper-catalyzed arylation
was successfully applied to the synthesis of polyfluori-
nated biphenyls from polyfluoroarenes. Herein, arenes
containing two or more fluorine atoms in the ring
reacted with iodo-, bromo-, and (in some cases)
chloroarenes in the presence of copper salts and bases.
The reaction was most efficient when most acidic
C–H bond contiguous to two fluorine atoms was
involved [37–39].
Cross-coupling reactions of polyfluoroarenes in-
volving cleavage of the C–F bond (which is the
1388

SYNTHESIS OF PERFLUORINATED BIARYLS
1389
Scheme 1.
ZnX
DMF, 125°C, 22 h
56%
F
+
F
F3C
CF3
F
F
F3C
F3C
1
2
3
ZnX
DMF, 125°C, 22 h
59%
F
+
F
N
N
F
F
N
N
4
5
6
X = Cl, C5F4N, 4-F3CC6H4.
of 4, and the yield of octafluoro-4,4′-bipyridine (6) was
59% (Scheme 1).
The above considered reactions allow preparation
of polyfluorinated biaryls. Syntheses of perfluorinated
biaryls with the use of Pd, Ni, or Cu catalysts have not
been reported. Symmetrical perfluorobiaryls are most
commonly synthesized by the Ullmann reaction [40,
41]. Unsymmetrical perfluorobiaryls were obtained
by reactions of perfluoroaryllithiums and perfluoro-
arylmagnesium halides as nucleophiles with perfluoro-
arenes. However, these reactions were accompanied by
side formation of new perfluorobiaryls and high-
molecular-weight compounds due to instability of
organometallic reagents which decomposed via elimi-
nation of metal halide with formation of intermediate
perfluoroarynes [41, 42].
By reacting organozinc compounds 7a with octa-
fluorotoluene (2), decafluoro-m-xylene (8), and pen-
tafluorobenzonitrile (9) we obtained, respectively,
nonafluoro-4-(trifluoromethyl)biphenyl (10), octa-
fluoro-2,4-bis(trifluoromethyl)biphenyl (11), and nona-
fluorobiphenyl-4-carbonitrile (12) (Scheme 2).
As shown in [47], pentafluorophenylmagnesium
bromide reacts with pentafluoronitrobenzene (13) to
give nonafluoro-4-nitrobiphenyl (14, major product,
61%) and isomeric nonafluoro-2-nitrobiphenyl (15,
6%). The reactions of 7a and 7b with 13 also afforded
a mixture of compounds 14 and 15 at a ratio of ~3:1
(according to the 19F NMR data; Scheme 3). The
formation of 15 may be accounted for by coordination
involving the nitro group in the transition state.
We previously reported successful synthesis of
functionalized perfluoroarenes by reactions of per-
fluoroarylzinc compounds with electrophiles [43–46].
In the present work we studied reactions of perfluoro-
arylzinc compounds as nucleophiles with perfluoro-
arenes with a view to obtaining symmetrical and un-
symmetrical perfluorinated biaryls.
δ–
O
O
X
F
N
Zn
F
F
δ'–
2,3,5,6-Tetrafluoro-4-trifluoromethylphenylzinc
compounds 1 reacted with octafluorotoluene (2) in
DMF at 125°C to give 4,4′-bis(trifluoromethyl)octa-
fluorobiphenyl (3) as the major product and a small
amount of 1,2,4,5-tetrafluoro-3-trifluoromethylben-
zene (Scheme 1). The reactions of tetrafluoropyridyl-
zinc compounds 4 with pentafluoropyridine (5) at
70°C were characterized by a low conversion; raising
the temperature to 125°C ensured complete conversion
F
F
F
This assumption is consistent with the ability of
organozinc compounds to form organozincates [48].
Zinc(II) cation is characterized by a higher electron
affinity (9.39 eV) than Mg2+ (7.64 eV) [49]. This
difference may also be taken into account to rationalize
Scheme 2.
Z
Z
DMF, 125–140°C
6.5–44 h
ZnX
C6F5
F
+
F
F
Y
Y
7a
2, 8, 9
10–12
X = Cl, C6F5; 2, 10, Y = CF3, Z = F; 8, 11, Y = Z = CF3; 9, 12, Z = F, Y = CN.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 10 2015

VINOGRADOV, PLATONOV
1390
Scheme 3.
ZnX
NO2
NO2
NO2
DMF, 125°C, 22 h
F
+
F
F
+
F
C6F5
C6F5
7a, 7b
13
14
15
7b, X = Br, C6F5.
the formation of a larger amount of isomer 15 in the
reaction of 13 with 7a and 7b. The effect of the solvent
requires a separate study.
relative to 3 and 10 are determined by higher reactivity
of 5 (relative to 2) in nucleophilic aromatic substitution
reactions [41, 50]. Other factors reducing the yields of
perfluorobiaryls may be side formation of perfluoro-
terphenyls at elevated temperature and partial decom-
position of the solvent (DMF), which could favor
formation of other by-products and tarring.
Compound 1 reacted with arenes 8 and 9 to afford
perfluoro(2,4,4′-trimethylbiphenyl) (16) and perfluoro-
(4′-methylbiphenyl-4-carbonitrile) (17), respectively
(Scheme 4). Likewise, perfluoro[4-(4-methylphenyl)-
pyridine] (18) and perfluoro(4-phenylpyridine) (19)
were obtained in the reactions of organozinc com-
pounds 1 and 7a with hetarene 5 (Scheme 5).
In summary, we have synthesized symmetrical
perfluorinated biaryls and some their unsymmetrical
analogs by reaction of perfluoroarylzinc compounds
with perfluoroarenes. These reactions demonstrate new
synthetic potential of perfluoroarylzinc reagents which
still remain poorly studied. The synthesis of symmet-
rical and especially unsymmetrical perfluorinated
biaryls extends the scope of their application in
chemical studies and practice.
Scheme 4.
CF3
DMF, 125°C, 5 h
1
1
+
+
8
9
F3C
F3C
CF3
CN
F
F
49%
16
DMF, 125°C, 5 h
35%
EXPERIMENTAL
F
F
Analytical and spectral measurements were per-
formed at the Collective Chemical Service Center,
Siberian Branch, Russian Academy of Sciences. The
19F NMR spectra were recorded on a Bruker AV 300
spectrometer at 282.4 MHz; chloroform-d or ace-
tone-d6 was added to the reaction mixtures containing
organozinc compounds in DMF; in other cases, carbon
tetrachloride was used as solvent, and hexafluoroben-
zene, as standard. The IR spectra were measured from
solutions in carbon tetrachloride on a Bruker Vector 22
spectrometer. The UV spectra were recorded from
solutions in ethanol on a Hewlett Packard 8453 spec-
trophotometer. The molecular weights and elemental
17
The site of substitution in the reactions of 1, 4, and
7 with perfluoroarenes 2, 5, 8, 9, and 13 is consistent
with the orientation observed in nucleophilic reactions
of the same perfluoroarenes [50]. Therefore, these
reactions may be regarded as nucleophilic aromatic
substitution. Reduced nucleophilicity of 7a may be
responsible for the lower yields of 10–12 than the
yields of 3, 16, and 17 in the reactions with organozinc
reagent 1. However, the assumed difference in the
reactivities of 1 and 7a needs further confirmation. It is
quite probable that the higher yields of 18 and 19
Scheme 5.
ZnX
DMF, 125°C, 22 h
79%
F
5
+
F
F
N
CF3
F3C
1
18
C6F5
ZnX
DMF, 125°C, 22 h
62%
F
+
5
F
N
7a
19
1, R = CF3; 7a, R = F; X = Cl, 4-RC6F4.
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SYNTHESIS OF PERFLUORINATED BIARYLS
1391
compositions were determined from the high-resolu-
tion mass spectra which were obtained on a Thermo
Electron Corporation DFS instrument (electron impact,
70 eV). GC/MS analyses were obtained on a Hewlett
Packard G1800A GC/MS system consisting of an HP
5890 Series II gas chromatograph and an HP 5971
mass-selective detector (electron impact, 70 eV; HP-5
capillary column, 30 m×0.25 mm; carrier gas helium,
flow rate 1 mL/min; injector temperature 280°C, ion
source temperature 173°C; a.m.u. range 30–650). GC
analysis was performed on a Hewlett Packard HP 5980
chromatograph equipped with an HP-5 quartz capillary
column (30 m×0.52 mm, film thickness 2.6 μm) and
a thermal conductivity detector. The melting point
were measured on a Kofler hot stage.
(Irel, %): 435 (12), 434 (100) [M]+, 415 (37), 384 (41),
28 (17), 18 (11). Found: m/z 433.9770 [M]+. C14F14.
Calculated: [M]+ 433.9771.
Octafluoro-4,4′-bipyridine (6). A mixture of
5.78 g (10 mmol) of 4 and 1.69 g (10 mmol) of 5 in
DMF was heated for 8 h at 70°C in a closed flask. The
mixture contained (19F NMR) compounds 4, 5, 6, and
21 at a ratio of 40:46:12:2. The mixture was then
heated for 22 h at 125°C in a sealed ampule. After
cooling to room temperature, the mixture contained
~94% of 6. Sublimation at 95–100°C (~2 mm)
(method B) gave 1.78 g (59%) of 6 (GC purity 98%),
mp 82–83°C (from benzene); published data [53]:
mp 81–82°C. 19F NMR spectrum, δF, ppm: 23.2 m (4F,
3-F, 3′-F, 5-F, 5′-F), 74.8 m (4F, 2-F, 2′-F, 6-F, 6′-F)
[53]. Mass spectrum, m/z (Irel, %): 301 (10), 300 (100)
[M]+, 255 (12), 231 (10), 205 (12). Found: m/z
299.9935 [M]+. C10F8N2. Calculated: [M]+ 299.9928.
Solutions of perfluoroarylzinc compounds 1, 4, 7a,
and 7b were prepared as described in [43]; these
solutions contained, respectively, 93% of 1 and 7% of
1,2,4,5-tetrafluoro-3-trifluoromethylbenzene (20), 98%
of 4 and 2% of 2,3,5,6-tetrafluoropyridine (21), 91% of
7a and 9% of pentafluorobenzene (22), and 94% of 7b
and 6% of 22.
Nonafluoro-4-(trifluoromethyl)-1,1′-biphenyl
(10). The reaction mixture obtained from 7.30 g
(10 mmol) of 7a and 4.72 g (20 mmol) of 2 (reaction
time 44 h) contained compounds 7a, 10, and 22 at
a ratio of 36:46:18 (with no account taken of 2).
Treatment according to method C gave 1.26 g of
a product containing (GC) 94% of 10. Yield 31%,
mp 33–34°C (from EtOH; sealed capillary); published
data [42]: mp 32–33°C (from EtOH). 19F NMR spec-
trum, δF, ppm: 2.2 m (2F, 3′-F, 5′-F), 13.3 t (1F, 4′-F,
J4′,3′(5′) = 20.7 Hz), 23.1 m (2F), 24.7 m (2F), 26.1 m
(2F), 105.2 t [3F, CF3, J(CF3–3(5)-F) = 22.0 Hz] [42].
Mass spectrum, m/z (Irel, %): 385 (12), 384 (100) [M]+,
365 (33), 334 (55), 296 (15), 265 (13). Found:
m/z 383.9807 [M]+. C13F12. Calculated: [M]+ 383.9803.
General procedure for reactions of polyfluoro-
arylzinc compounds with perfluoroarenes. An am-
pule was charged with a solution of organozinc reagent
and perfluoroarene, and the ampule was sealed and
heated at 125°C for a time indicated below. The
ampule was cooled to room temperature and opened,
and the mixture was analyzed by 19F NMR. The mix-
ture was then treated with 100 mL of water, and the
products were isolated according to one of the follow-
ing procedures: A: the precipitate was filtered off and
sublimed; B: the mixture was extracted with methylene
chloride (3×5 mL), the extract was dried over CaCl2
and evaporated, and the residue was sublimed; C: the
mixture was steam-distilled, and the organic phase was
separated and kept under reduced pressure to remove
volatile impurities.
Octafluoro-2,4-bis(trifluoromethyl)-1,1′-bi-
phenyl (11). The reaction mixture obtained from
7.63 g (10.0 mmol) of 7a and 8.16 g of a perfluoro-
xylene mixture containing 5.72 g (20.0 mmol) of 8 (8–
decafluoro-p-xylene 2.5:1, 19F NMR) (reaction time
6.5 h) was treated according to method C. Yield of 11
0.87 g (20%; purity 95%). IR spectrum, ν, cm–1: 1657,
1641, 1601, 1528, 1508, 1483, 1375, 1358, 1310,
1242, 1167, 997, 928. UV spectrum: λmax 279 nm
(logε 3.82). 19F NMR spectrum, δF, ppm: 2.0 m (2F,
3′-F, 5′-F), 13.0 t (1F, 4′-F, J4′,3′(5′) = 20.7 Hz), 23.3 m
Octafluoro-4,4′-bis(trifluoromethyl)-1,1′-bi-
phenyl (3). The reaction mixture obtained from 8.13 g
(10 mmol) of 1 and 2.36 g (10 mmol) of 2 (reaction
time (22 h) contained (hereinafter, according to the
19F NMR data) compounds 2, 3, and 20 at a ratio of
31:63:6. Sublimation at 100–105°C (~2 mm) (method
A) gave 2.62 g (56%) of 3 (purity 92% according to the
GC data), mp 100–102°C (from EtOH; sealed capil-
lary); published data [51]: mp 98–100°C. 19F NMR
spectrum, δF, ppm: 23.6 m (4F, 3-F, 3′-F, 5-F, 5′-F),
26.5 m (4F, 2-F, 2′-F, 6-F, 6′-F), 105.2 t [6F, CF3,
J(CF3, 3(5)-F) = 22.0 Hz] [52]. Mass spectrum, m/z
(2F, 2′-F, 6′-F), 27.8 br.d.d (1F, 6-F, J6,5 = 21.3, J6,3
=
14.6 Hz), 37.2 q [1F, 5-F, J(5-F, CF3) ≈ 23.0 Hz],
49.6 sept.d.d [1F, 3-F, J(3-F, 2-CF3) ≈ 22.8, J3,6 = 14.6,
J3,5 = 1.9 Hz], 104.5 d [3F, 2-CF3, J(2-CF3, 3-F) =
23.2 Hz], 105.0 t [3F, 4-CF3, J(4-CF3, 3(5)-F) =
22.9 Hz]. Mass spectrum, m/z (Irel, %): 435 (15), 434
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VINOGRADOV, PLATONOV
1392
(100) [M]+, 415 (33), 384 (13), 365 (35), 346 (24), 327
(10), 315 (11), 296 (16). Found, %: C 38.40; F 61.35.
m/z 433.9768 [M]+. C14F14. Calculated, %: C 38.73;
F 61.27. [M]+ 433.9771.
(10.0 mmol) of 1 and 8.16 g of a mixture of per-
fluoroxylenes containing 5.72 g (20.0 mmol) of 8
(meta/para ratio 2.5:1) (reaction time 5 h) was treated
according to method B (sublimation at 100–105°C,
~4 mm). Yield of 16 2.39 g (49%), purity 96% (GC).
IR spectrum, ν, cm–1: 1645, 1601, 1504, 1491, 1360,
1327, 1248, 1223, 1188, 1167, 995, 935. UV spectrum:
λmax 280 nm (logε 3.63). 19F NMR spectrum, δF, ppm:
Nonafluoro-1,1′-biphenyl-4-carbonitrile (12).
The reaction mixture obtained from 2.00 g (3.4 mmol)
of 7a and 1.32 g (6.8 mmol) of 9 (reaction time 22 h)
was treated according to method B (sublimation at 95–
100°C, ~2 mm). The product was 0.60 g of a mixture
containing 43% of 9 and 57% of 12 (yield 29%). It was
kept under reduced pressure to remove volatile com-
pounds and recrystallized from hexane to obtain
an analytical sample of 12 (GC purity 99%), mp 52–
53°C. IR spectrum, ν, cm–1: 2249, 1657, 1595, 1529,
23.5 m (2F), 25.1 m (2F), 27.9 br.d.d (1F, 6-F, J6,5
=
21.1, J6,3 = 14.2 Hz), 37.8 q [1F, 5-F, J(5-F, CF3) =
22.8 Hz], 50.2 sept.d.d [1F, 3-F, J(3-F, 2-CF3) ≈ 22.4,
J3, 6 = 14.2, J3, 5 = 2.6 Hz], 104.4 d [3F, 2-CF3,
J(2-CF3, 3-F) = 22.4 Hz], 104.9 t (3F, CF3, J =
22.9 Hz), 105.1 t (3F, CF3, J ≈ 22.0 Hz). Mass spec-
trum, m/z (Irel, %): 485 (18), 484 (100) [M]+, 465
(49), 434 (14), 415 (18), 377 (15), 365 (10), 346 (22),
327 (14), 69 (21). Found, %: C 36.94; F 62.60.
m/z 483.9736 [M]+. C15F16. Calculated, %: C 37.21;
F 62.79. [M]+ 483.9739.
1490, 1292, 1143, 1042, 1005, 982. UV spectrum, λmax
,
19
nm (logε): 202 (4.35), 249 (4.29). F NMR spectrum,
δF, ppm: 2.5 m (2F, 3′-F, 5′-F), 13.8 t.t (1F, 4′-F,
J4′,3′(5′) = 20.7, J4′,2′(6′) = 3.5 Hz), 24.8 m (2F, 2′-F, 6′-F),
26.8 m (2F, 2-F, 6-F), 30.6 m (2F, 3-F, 5-F). Mass
spectrum, m/z (Irel, %): 342 (11), 341 (100) [M]+, 272
(16). Found, %: C 45.91; F 50.69; N 4.18.
m/z 340.9883 [M]+. C13F9N. Calculated, %: C 45.77;
F 50.12; N 4.11. [M]+ 340.9882.
Perfluoro(4′-methyl-1,1′-biphenyl-4-carboni-
trile) (17). The reaction mixture obtained from 3.20 g
(4.0 mmol) of 1 and 1.55 g (8.0 mmol) of 9 (reaction
time 5 h) contained compounds 17 and 20 at a ratio of
94:6 (compound 9 was not taken onto account). The
mixture was treated according to method B (sublima-
tion at 120–125°C, ~4 mm) to isolate 1.05 g of a mix-
ture of 20% of 9 and 80% of 17 (19F NMR). Evacua-
tion at 2 mm gave 0.55 g (35%) of 17 with a purity of
97% (GC). IR spectrum, ν, cm–1: 2249, 1663, 1651,
1499, 1483, 1346, 1310, 1194, 1163, 1007, 982, 712.
UV spectrum, λmax, nm (logε): 246 (4.41), 289 (3.75).
19F NMR spectrum, δF, ppm: 24.0 m (2F), 26.7 m (2F),
27.5 m (2F), 31.4 m (2F, 3-F, 5-F), 105.1 t [3F, CF3,
J(CF3, 3′(5′)-F) = 22.0 Hz]. Mass spectrum, m/z
(Irel, %): 392 (16), 391 (100) [M]+, 372 (27), 341 (41),
303 (14), 272 (17). Found, %: C 42.87; F 53.34;
N 3.77. m/z 390.9855 [M]+. C14F11N. Calculated, %:
C 42.99; F 53.43; N 3.58. [M]+ 390.9850.
Reaction of organozinc compounds 7 with penta-
fluoronitrobenzene (13). a. A solution of 2.00 g
(3.4 mmol) of 7a and 1.45 g (6.8 mmol) of 13 was
heated for 22 h at 125°C in a sealed ampule. The
mixture contained compounds 14, 15, and 22 at a ratio
of ~60 : 20 : 20 (compound 13 was not taken into
account). The mixture was treated according to method
B, and removal of the solvent gave 2.04 g of a mixture
containing (GC/MS) 32% of 13, 38% of 14, and
12% of 15.
Nonafluoro-4-nitro-1,1′-biphenyl (14). Yield
63%. 19F NMR spectrum, δF, ppm: 2.1 m (2F, 3′-F,
5′-F), 13.6 t.t (1F, 4′-F, J4′,3′(5′) = 20.7, J4′,2′(6′) = 3.9 Hz),
17.5 m (2F, 3-F, 5-F), 25.7 m (2F, 2′-F, 6′-F), 28.0 m
(2F, 2-F, 6-F) [52].
Nonafluoro-2-nitro-1,1′-biphenyl (15). 19F NMR
spectrum, δ, ppm: 2.2 m (2F, 3′-F, 5′-F), 13.4 t.t (1F,
4′-F, J4′, 3′(5′) = 20.7, J4′, 2′(6′) = 3.0 Hz), 15.5 m (1F),
16.6 m (1F), 20.3 m (1F), 24.3 m (2F, 2′-F, 6′-F),
29.4 m (1F) [54]. Found: m/z 361 [M]+.
Perfluoro[4-(4-methylphenyl)pyridine] (18). The
reaction mixture obtained from 3.94 g (5.0 mmol) of 1
and 1.69 g (10.0 mmol) of 5 (reaction time 22 h)
contained compounds 18 and 20 at a ratio of 94:6
(compound 5 was not taken into account). The mixture
was treated according to method B (sublimation at
120°C, ~4 mm) to isolate 1.45 g (79%) of 18 with
a purity of 98% (GC), mp 72–74°C (from EtOH). IR
spectrum, ν, cm–1: 1643, 1493, 1470, 1342, 1279,
b. A solution of 2.78 g (3.4 mmol) of 7b and 1.45 g
(6.8 mmol) of 13 was heated for 22 h at 125°C in
a sealed ampule. The mixture contained (19F NMR)
compounds 14, 15, and 22 at a ratio of 57 :20 :23
(compound 13 was not taken into account).
1192, 1165, 1038, 1003, 962, 714. UV spectrum, λmax
,
19
nm (logε): 229 (4.16), 283 (3.82). F NMR spectrum,
δF, ppm: 22.9 m (2F), 24.1 m (2F), 26.7 m (2F), 74.7
Perfluoro(2,4,4′-trimethyl-1,1′-biphenyl) (16).
The reaction mixture obtained from 8.00 g
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SYNTHESIS OF PERFLUORINATED BIARYLS
1393
10. Budd, P.M., Ghanem, B.S., Makhseed, S., Mc-
Keown, N.B., Msayib, K.J., and Tattershall, C.E., Chem.
Commun., 2004, no. 2, p. 230.
11. Taylor, R.G.D., Carta, M., Bezzu, C.G., Walker, J.,
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Lett., 2014, vol. 16, p. 1848.
(2F, 2-F, 6-F), 105.0 t [3F, CF3, J(CF3, 3′(5′)-F) =
22.0 Hz]. Mass spectrum, m/z (Irel, %): 368 (14), 367
(100) [M]+, 348 (32), 317 (57), 298 (11), 279 (18), 248
(21), 69 (20), 28 (13). Found, %: C 39.63; F 56.95;
N 4.27. m/z 366.9855 [M]+. C12F11N. Calculated, %:
C 39.26; F 56.93; N 3.82. [M]+ 366.9855.
12. Lafrance, M., Rowley, Ch.N., Woo, T.K., and
Perfluoro(4-phenylpyridine) (19). The reaction
mixture obtained from 7.30 g (10 mmol) of 7a and
3.38 g (20 mmol) of 5 (reaction time 22 h) contained
compounds 7a, 19, and 22 at a ratio of 7 : 78 : 15
(compound 5 was not taken into account). Treatment
of the mixture according to method C gave 1.97 g
(62%) of 19 with a purity of 95% (GC). The product
was purified by sublimation at 90°C (~4 mm),
followed by recrystallization from ethanol to obtain
a sample with a purity of 99% (GC), mp 103–104°C
(sealed capillary); published data [54]: mp 98–99°C.
19F NMR spectrum, δF, ppm: 2.6 m (2F, 3′-F, 5′-F),
14.1 t.t (1F, 4′-F, J4′,3′,5′ = 21.0, J4′,2′,6′ = 3.8 Hz), 22.4 m
(2F), 24.9 m (2F), 74.0 m (2F, 2-F, 6-F) [53]. Mass
spectrum, m/z (Irel, %): 318 (12), 317 (100) [M]+, 272
(12), 248 (18), 28 (15). Found: m/z 316.9894 [M]+.
C11F9N. Calculated: [M]+ 316.9882.
Fagnou, K., J. Am. Chem. Soc., 2006, vol. 128, p. 8754.
13. Lafrance, M., Shore, D., and Fagnou, K., Org. Lett.,
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16. Song, Y., Lin, F.-Y., Yin, F., Hensler, M.,
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This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 15-03-08869a).
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