M. Nishida et al. / Journal of Fluorine Chemistry 131 (2010) 1314–1321
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4.3. Reaction of octafluorotoluene (1b) with 2 equiv. of C6F5Si(CH3)3
solution of 1b (249 mg, 1.05 mmol) and C6F5Si(CH3)3
4.5. Reaction of pentafluorobenzonitrile (1d) with 2 equiv. of
C6F5Si(CH3)3
A
(506 mg, 2.11 mmol) with a 1 ml of anhydrous DMF was placed
in a 10 ml Teflon vessel, and then a catalytic amount (15 mg) of
KHF2 was added vigorously stirring with a magnetic stirrer. After
stirring at room temperature for 3 h, the reaction mixture turned to
a light-yellow suspension. A white solid was collected by filtration.
The white solid consisted of a mixture of 32% of 2b, 32% of 3b, 9% of
4b determined by 19F NMR spectroscopy and MS analysis. While 3b
was isolated by Kur-gel Rohr distillation, 2b and 4b were collected
as a mixture with 3b, so they were analyzed as a mixed form. The
CF3 peaks of the 19F NMR also indicated possible formation of
small amounts of isomers 5b and 6b, but their 19F NMR spectra
could not be assigned because of overlapping aromatic ring
fluorine peaks.
A solution of 1d (151 mg, 0.78 mmol) and C6F5Si(CH3)3
(378 mg, 1.57 mmol) with a 3 ml of anhydrous DMF was placed
in a 10 ml Teflon vessel, and then a catalytic amount (12 mg) of
KHF2 was added vigorously stirring with a magnetic stirrer. After
stirring at room temperature for 3 h, the reaction mixture turned to
an orange suspension. The Kur-gel Rohr distillation provided a
mixture of 63% of 2d, 20% of 6d, and 9.1% of 7d determined by 19
F
NMR spectroscopy and MS analysis.
4.5.1. Perfluoro-[1,10;30,100]terphenyl-40-carbonitrile (6d)
19F NMR (282 MHz, CDCl3):
d
ꢀ109.08 (1F, m, 20-F), ꢀ124.85
(1F, m, 60-F), ꢀ130.15 (1F, m, 50-F), ꢀ137.01 (2F, m, 2,6-F), ꢀ137.82
(2F, m, 200,500-F), ꢀ148.29 (1F, t m, J = 19.4 Hz, 400-F), ꢀ148.35 (1F, t
m, J = 21.5 Hz, 4-F), ꢀ159.61 (2F, m, 300,500-F), ꢀ159.86 (2F, m, 3,5-
F); QP-MS (m/z, %): 489 [M+, 100], 420 [M+-CF3, 11], 244 (15).
4.3.1. Perfluoro-(4-methly-[1,10:40,100]terphenyl) (3b)
19F NMR (282 MHz, CDCl3):
d
ꢀ56.96 (3F, t, J = 22.4 Hz, 4-CF3),
ꢀ135.52 (2F, m, 2 F, 2,6-F), ꢀ136.65 (2F, m, 20,60-F), ꢀ136.77 (2F,
m, 30,50-F), ꢀ137.34 (2F, m, 200,600-F), ꢀ139.07 (2F, m, 3,5-F),
ꢀ149.57 (1F, t m, J = 19.8 Hz, 1 F, 400-F), ꢀ160.55 (2F, 2 F, 300,500-F);
4.5.2. Perfluoro-(50-phenyl-[1,10;30,100]terphenyl-20-carbonitrile) (7d)
19F NMR (282 MHz, CDCl3):
d
ꢀ100.54 (2F, m, 40,60-F), ꢀ136.85
(2F, m, 2000,6000-F), ꢀ137.61 (4F, m, 2,6-F and 200,600-F), ꢀ148.38 (1F, t
m, J = 19.5 Hz, 4000-F), ꢀ148.50 (2F, t m, J = 21.5 Hz, 4-F and 400-F),
ꢀ159.68 (4F, m, 3,5-F and 300,500-F), ꢀ159.81 (2F, m, 3000,5000-F); QP-
MS (m/z, %): 637 [M+,100], 568 [M+-CF3, 11], 318 (39), 284 (16).
13C NMR (75.42 MHz, CDCl3):
d 101.74, 108.15, 109.30, 110.93,
112.10, 114.60, 120.56, 138.09, 142.93, 144.15, 144.44, 144.44,
144.52; QP-MS (m/z, %): 630 [M+, 100], 315 [C6F5C6F4+, 48]. 532
[M+, 100], 512 [M+-F, 13], 481 [M+-CF2, 16], 266 (13), 241 (19), 69
(18).
4.6. Reaction of decafluoro-(1,1-biphenyl) (1a) with 10 equiv. of
C6F5Si(CH3)3
4.3.2. Perfluoro-(4-methyl-[1,10:40,100:400,1000]quaterphenyl) (4b)
19F NMR (282 MHz, CDCl3):
d
ꢀ56.94 (3F, t, J = 21.7 Hz, 1-CF3),
A solution of 1a (78 mg, 0.23 mmol) and C6F5Si(CH3)3
ꢀ135.42 (2F, m, 2,6-F), ꢀ136.20 (2F, m, 20,60-F), ꢀ136.50 (2F, m,
200,600-F), ꢀ136.75 (2F, m, 30,50-F), ꢀ136.78 (2F, m, 300,500-F),
ꢀ137.31 (2F, m, 2000,6000-F), ꢀ139.00 (2F, m, 3,5-F), ꢀ149.49 (1F,
t, J = 21.5 Hz, 4000-F), ꢀ160.40 (2F, m, 3000,5000-F); 13C NMR
(574 mg, 2.39 mmol) with 3 ml of anhydrous DMF was placed
in a 10 ml Teflon vessel, and then a catalytic amount (5 mg) of
KHF2 was added vigorously stirring with a magnetic stirrer. After
stirring at room temperature for 10 min, the DMF solution turned
to an orange solution, and then to a white suspension for 5 h.
After constant stirring for 24 h, the white solid formed (421 mg)
(75.42 MHz, CDCl3):
d 101.61, 108.38, 108.66, 109.01, 109.54,
110.87, 112.11, 117.35, 120.52, 138.06, 142.87, 114.18, 144.24,
144.33, 144.42, 144.50, 144.59; QP-MS (m/z, %): 680 [M+, 100], 340
(43), 330 (17), 315 (30), 298 (12), 69 (18).
was collected by filtration, washed with DMF, and dried. The 19
NMR and TOF–MS analyses indicated that the white solid
F
consisted of 8a.
4.4. Reaction of pentafluoronitrobenze (1c) with 2 equiv. of
C6F5Si(CH3)3
Data of 8a: 19F NMR (CDCl3, 282 MHz):
d
ꢀ136.60, ꢀ136.78,
ꢀ137.01, ꢀ137.32 (22F, m), ꢀ149.63 (2F, t m, J = 19.5 Hz), ꢀ160.51
(4F, m); TOF–MS (Mꢀ): 611 [26, C24F17], 630 [37, C24F18(n = 2)], 759
[100, C30F21], 778 [70, C30F22 (n = 3)], 907 [67, C36F25], 926 [26,
C36F26 (n = 4)], 1055 [12, C42F29], 1074 [4.4, C42F30 (n = 5)], 1203
[4.3, C48F33], 1222 [2.0, C48F34 (n = 6)], 1352 [3.5, C54F37], 1371 [2.3,
A solution of 1c (156 mg, 0.73 mmol) and C6F5Si(CH3)3 (359 mg,
1.49 mmol) with a 2 ml of anhydrous DMF was placed in a 10 ml
Teflon vessel, and then a catalytic amount (12 mg) of KHF2 was
added vigorously stirring with a magnetic stirrer. After stirring at
room temperature for 3 h, the reaction mixture turned to an orange
suspension. The Kur-gel Rohr distillation provided a mixture of 63%
of 2c, 20% of 6c, and 9% of 7c determined by 19F NMR spectroscopy
and MS analysis.
C
54F38 (n = 7)].
4.7. Reaction of octafluorotoluene (1b) with C6F5Si(CH3)3 with
10 equiv. of C6F5Si(CH3)3
A solution of 1b (56 mg, 0.24 mmol) and C6F5Si(CH3)3 (567 mg,
2.36 mmol) with a 3 ml of anhydrous DMF was placed in a 10 ml
Teflon vessel, and then a catalytic amount (5 mg) of KHF2 was
added vigorously stirring with a magnetic stirrer. After stirring at
room temperature for 1 h, the DMF solution turned to a white
suspension, and a white solid precipitated for 3 h. After constant
stirring for 24 h, the white solid (160 mg) was collected by
filtration, washed with DMF, and dried under vacuum. The 19F
NMR and TOF–MS analyses indicated that the white solid consisted
of a mixture of 8b and 9b.
4.4.1. Perfluoro-(40-nitro-[1,10;30,100]terphenyl) (6c)
19F NMR (282 MHz, CDCl3,):
d
ꢀ108.96 (1F, m, 20-F), ꢀ123.04
(1F, m, 60-F), ꢀ137.06 (2F, m, 200,600-F), ꢀ138.31 (2F, m, 2,6-F),
ꢀ144.93 (1F, m, 50-F), ꢀ148.33 (1F, t m, J = 21.5 Hz, 400-F), ꢀ148.88
(1F, t m, J = 21.5 Hz, 4-F), ꢀ159.82 (2F, m, 300,500-F), ꢀ159.89 (2F, m,
3,5-F); QP-MS (m/z, %): 509 [M+, 100], 434 (59), 413 (52), 403 (67),
296 (50), 265 (20), 140 (37), 93 (44), 69 (52).
4.4.2. Perfluoro-(20-nitro-50-phenyl-[1,10;30,100]terphenyl) (7c)
19F NMR (282 MHz, CDCl3):
d
ꢀ99.23 (2F, m, 20,60-F), ꢀ136.83
Data of the polymerized products (the mixture of 8b and 9b):
(2F, m, 2000,6000-F), ꢀ138.17 (4F, m, 2,6-F and 200,600-F), ꢀ148.44 (1F, t
m, J = 21.5 Hz, 4000-F), ꢀ148.93 (2F, t m, J = 21.5 Hz, 4-F and 400-F),
ꢀ159.86 (4F, m, 3,5-F and 300,500-F), ꢀ159.94 (2F, m, 3000,5000-F); QP-
MS (m/z, %): 657 [M+, 71], 582 (69), 532 (48), 492 (45), 246 (36),
140 (82), 93 (58), 69 (62).
19F NMR (CDCl3, 282 MHz):
d
ꢀ56.94 (3F, t, J = 21.5 Hz), ꢀ58.20 (3F,
br d, J = 19.5 Hz), ꢀ109.40 (1F, br s), ꢀ111.39 (1F, m), ꢀ136.0 to
ꢀ138.0 (64F, m), ꢀ149.55 (6F, m), ꢀ160.42 (12F, m); TOF–MS
(Mꢀ): 680 [45, C25F20, (n = 3)], 828 [100, C31F24 (n = 4)], 976 [53,
C37F28 (n = 5)], 1124 [17, C43F32 (n = 6)], 1272 [6.7, C49F36