V.V. Bardin et al. / Journal of Fluorine Chemistry 135 (2012) 114–128
123
(CF3)2CFCBB CH. 19F NMR (aHF, 0 8C):
d
ꢂ75.9 (d, 3J(CF3,
F5B) = 292 Hz, 1F, F5A), ꢂ125.2 (ddddd, 3J(F5B, F4B) = 3 Hz, 3J(F5B
,
,
,
,
F3) = 10 Hz, 6F, 2CF3), ꢂ167.4 (dsept, 4J(F3, H1) = 6 Hz, 3J(F3,
CF3) = 10 Hz, 1F, F3) (cf. with 19F NMR spectrum in ether [23]).
F4A) = 8 Hz, 4J(F5B
,
F3B) = 15 Hz, 4J(F5B
,
F3A) = 19 Hz, 2J(F5B
F5A) = 292 Hz, 1F, F5B), ꢂ121.9 (br m, Dn1/2 = 72 Hz, d, 2J(F1A
F1B) = 319 Hz, 1F, F1A), ꢂ124.9 (br m, Dn1/2 = 71 Hz, d, 2J(F1B
4.2.5. Reaction of K[C4F9CF55CFCBB CBF3]
F1A) = 319 Hz, 1F, F1B), ꢂ134.1 (m, 1F, F2), ꢂ150.0 (q (1:1:1:1), 1J(F,
B) = 40 Hz, 3F, BF3).
Anal. Calcd for C6BClF15K (442.40): C, 16.29; Cl, 8.01; F, 64.42.
Found: C, 16.3; Cl, 7.6; F, 63.9.
A. A solution of K[C4F9CF55CFCBB CBF3] (cis:trans = 45:55) (49 mg,
0.12 mmol) in 27% aq HF (0.5 mL) was maintained at ꢀ20 8C for
2 d. The periodic control by the 11B and 19F NMR spectroscopy
displayed no reaction.
4.3.2. Reaction of K[cis-C2F5CF55CFBF3]
A solution of K[cis-C2F5CF55CFBF3] (327 mg, 1.14 mmol) in aHF
(1 mL) was cooled to ꢀ0 8C and N-chlorosuccinimide (157 mg,
1.18 mmol) was added in one portion. The solution was stirred at
ꢀ20 8C for 1 h (no reaction), 24 h (37% conversion), 55 h (73%
conversion), and 102 h (100% conversion). KF (2–3 g) was added
and the slurry was diluted with water (1:1, v/v). The suspension
was extracted with ether (4ꢆ 1 mL). The combined extracts were
dried with KF and the solvent was removed under reduced
pressure. After additional drying in vacuum (13.3 hPa) K[C2F5CFCl–
CF2BF3] was obtained as a white solid (229 mg, 0.67 mmol, 59%).
B. A solution of K[C4F9CF55CFCBB CBF3] (cis:trans = 45:55) (41 mg,
0.10 mmol) and C6H5CF3 (5
mL, 0.04 mmol) (internal integral
standard) in aHF (0.6 mL) was kept at ꢀ20 8C for 0.5 h. The 11
B
and 19F NMR spectra displayed the quantitative conversion of
K[C4F9CF55CFCBB CBF3] to C4F9CF55CFCBB CH (cis:trans = 44:56)
and K[BF4].
K[cis-C4F9CF55CFCBB CBF3]. 11B NMR (27% aq HF):
d
ꢂ2.6 (br s).
19F NMR (27% aq HF):
d
ꢂ80.4 (tt, 3J(F8, F7) = 2 Hz, 4J(F8, F6) = 10 Hz,
3F, F8), ꢂ114.6 (d, 3J(F3, F4) = 10 Hz, 1F, F3), ꢂ115.2 (dt, 3J(F5,
F4) = 13 Hz, 4J(F5, F7) = 13 Hz, 2F, F5), ꢂ123.0 (m, 2F, F6), ꢂ125.4 (m,
2F, F7), ꢂ132.7 (purely resolved q, 3F, BF3), ꢂ142.6 (m, 1F, F4).
K[C2F5CFCl–CF2BF3]. 11B NMR (CD3CN):
d
2.8 (qt, 1J(B,
F) = 41 Hz, 2J(B, F1) = 20 Hz). 19F NMR (CD3CN):
d
ꢂ74.5 (ddd,
K[trans-C4F9CF55CFCBB CBF3]. 11B NMR (27% aq HF):
d
ꢂ2.6 (br s).
3J(F4, F3B) = 5 Hz, 3J(F4, F3A) = 7 Hz, 4J(F4, F2) = 11 Hz, 3F, F4), ꢂ114.1
19F NMR (27% aq HF):
d
ꢂ80.8 (tt, 3J(F8, F7) = 2 Hz, 4J(F8, F6) = 10 Hz,
(qdtd, 3J(F3A, F4) = 7 Hz, 3J(F3A, F2) = 8 Hz, 4J(F3A, F1) = 12 Hz, 2J(F3A
,
,
3F, F8), ꢂ116.8 (dtd, 3J(F5, F4) = 13 Hz, 4J(F5, F7) = 13 Hz, 4J(F5,
F3) = 25 Hz, 2F, F5), ꢂ123.7 (m, 2F, F6), ꢂ125.7 (m, 2F, F7), ꢂ132.7
(poorly resolved q, 3F, BF3), ꢂ135.2 (dt, 3J(F3, F4) = 140 Hz, 4J(F3,
F5) = 25 Hz, 1F, F3), ꢂ160.0 (d, 3J(F4, F3) = 140 Hz, 1F, F4) (cf. with
11B and 19F NMR spectra in CH3CN [23]).
F3B) = 284 Hz, 1F3A), ꢂ115.5 (qtd, 3J(F3B
,
F4) = 4 Hz, 4J(F3B
F1) = 12 Hz, 2J(F3B
,
F3A) = 284 Hz, 1F3B), ꢂ119.3 (br m, Dn1/
2 = 66 Hz, d, 2J(F1A, F1B) = 321 Hz, 1F, F1A), ꢂ122.2 (br m, Dn1/
2 = 67 Hz, d, 2J(F1B, F1A) = 321 Hz, 1F, F1B), ꢂ131.4 (m, 1F, F2),
ꢂ146.7 (q (1:1:1:1), 1J(F, B) = 40 Hz, 3F, BF3).
cis-C4F9CF55CFCBB CH. 19F NMR (aHF, 0 8C):
d
ꢂ79.6 (t, 4J(F8,
Anal. Calcd for C4BClF11K (342.39): C, 14.03; Cl, 10.35; F, 61.04.
Found: C, 13.8; Cl, 10.3; F, 60.2.
F6) = 10 Hz, 3F, F8), ꢂ114.5 (m, 2F, F5), ꢂ119.0 (dd, 3J(F3, F4) = 6 Hz,
4J(F3, H1) = 5 Hz, 1F, F3), ꢂ121.8 (m, 2F, F6), ꢂ124.4 (m, 2F, F7),
ꢂ138.6 (m, 1F, F4).
4.3.3. Reaction of K[CF3CBB CBF3]
trans-C4F9CF55CFCBB CH. 19F NMR (aHF, 0 8C):
d
ꢂ79.6 (t, 4J(F8,
N-chlorosuccinimide (300 mg, 2.25 mmol) was added in one
portion to a cold (ꢀ0 8C) stirred solution of K[CF3CBB CBF3] (200 mg,
1 mmol) in aHF (1 mL). The yellow solution was stirred for 1 h at
ꢀ0 8C and at ꢀ20 8C for 3 h. The 19F NMR spectrum showed the
presence of K[CF3CBB CBF3], K[(E)-CF3CCl55CFBF3], K[CF3CCl2–
CF2BF3], CF3CBB CH, and K[BF4] (molar ratio 100:13:34:31:172).
Afterstirringat ꢀ20 8C for33 hthe totalconversion of K[CF3CBB CBF3]
to K[CF3CCl2–CF2BF3], CF3CBB CH, and K[BF4] was achieved (signals of
[CF3CCl55CFBF3]ꢂ were no more detected). Volatiles were evaporat-
ed in vacuum and the semi-solid was stirred with charcoal (100 mg)
in water (2 mL) at ꢀ20 8C for 0.5 h and the solid was filtered off. The
filtrate was saturated with KF and extracted with acetonitrile (5ꢆ
1 mL). The combined extracts were treated with K2CO3 and the
solvent was evaporated to yield crude K[CF3CCl2–CF2BF3] (300 mg).
It was washed with CH2Cl2 (5ꢆ 1 mL) and stirred with 18-crown-6
(250 mg, 0.95 mmol) in CH2Cl2 (2 mL) for 1 h. After filtration the
solution was evaporated at ꢀ20 8C overnight. The solid was washed
with pentane (5ꢆ 2 mL) and ether (5ꢆ 2 mL) and dried in a vacuum
desiccatoroverSicapent1. Thesalt[Kꢄ18-crown-6][CF3CCl2–CF2BF3]
(230 mg, 0.40 mmol) was isolated.
F6) = 10 Hz, 3F, F8), ꢂ116.0 (m, 2F, F5), ꢂ122.5 (m, 2F, F6), ꢂ124.4
(m, 2F, F7), ꢂ138.3 (dt, 3J(F3, F4) = 139 Hz, 4J(F3, F5) = 26 Hz, 1F, F3),
ꢂ156.4 (d, 3J(F4, F3) = 139 Hz, 1F, F4).
4.2.6. Reaction of K[C4H9CBB CBF3]
A three-phase system of K[C4H9CBB CBF3] (69 mg, 0.36 mmol)
and C6F5H (20 mg, 0.12 mmol, internal integral standard) in CCl4
(0.7 mL) and 27% aq HF (1 mL) was stirred at ꢀ20 8C for 30 min. The
colorless organic phase at the bottom of the final three-phase
system contained C4H9CBB CH (quantitative yield) (1H NMR).
4.3. Reactions of perfluoroalkenyl- and
perfluoroalkynyltrifluoroborates with N-chlorosuccinimide in aHF
4.3.1. Reaction of K[trans-C4F9CF55CFBF3]
A solution of K[trans-C4F9CF55CFBF3] (166 mg, 0.43 mmol) in
aHF (1 mL) was cooled to ꢀ0 8C and N-chlorosuccinimide (70 mg,
0.52 mmol) was added in one portion. The solution was stirred at
ꢀ20 8C for 2 h (8% conversion), 20 h (83% conversion), and 48 h
(100% conversion). KF (2–3 g) was added and the slurry was diluted
with water (1:1, v/v). The suspension was extracted with ether (4ꢆ
1 mL). The combined extracts were dried with KF and the solvent
was removed under reduced pressure. After further drying in
vacuum (13.3 hPa) K[C4F9CFCl–CF2BF3] was obtained as a white
solid (114 mg, 0.25 mmol, 58%).
K[(E)-CF3CCl55CFBF3]. 19F NMR (aHF, 0 8C):
d
ꢂ60.7 (d, 4J(F3,
F1) = 25 Hz, 3F, F3), ꢂ105.4 (m, 1F, F1), ꢂ140.0 (q (1:1:1:1), 1J(F,
B) = 39 Hz, 3F, BF3).
K[CF3CCl2–CF2BF3]. 11B NMR (aHF, 0 8C):
d
ꢂ0.7 (m). 11B NMR
(CD3CN):
(CD3CN):
d
d
ꢂ0.5 (tq, 2J(B, F1) = 20 Hz, 1J(B, F) = 41 Hz). 13C{19F} NMR
122.3 (q (1:1:1:1), 1J(C-1, B) = 86 Hz, C-1), 120.9 (m, C-
K[C4F9CFCl–CF2BF3]. 11B NMR (CH3CN):
d
ꢂ0.6 (qt, 1J(B,
3), 86.4 (m, C-2). 19F NMR (aHF, 0 8C):
d
ꢂ71.7 (m, 3F, F3), ꢂ115.3
F) = 40 Hz, 2J(B, F1) = 20 Hz). 19F NMR (CH3CN):
d
ꢂ79.9 (tt, 4J(F6,
(m, 2F, F1), ꢂ145.1 (q (1:1:1:1), 1J(F, B) = 40 Hz, 3F, BF3). 19F NMR
F4) = 10 Hz, 3J(F6, F5) = 3 Hz, 3F, F6), ꢂ113.5 (md, 2J(F3A
,
(CD3CN):
d
ꢂ72.7 (tq, 4J(F3, F1) = 10 Hz, 5J(F3, BF3) = 6 Hz, 3F, F3),
F3B) = 295 Hz, 1F, F3A), ꢂ114.6 (md, 2J(F3B, F3A) = 295 Hz, 1F, F3B),
ꢂ115.6 (qq (1:1:1:1), 4J(F1, F3) = 10 Hz, 2J(F1, B) = 19 Hz, 2F, F1),
ꢂ117.9 (md, 2J(F4A, F4B) = 300 Hz, 1F, F4A), ꢂ119.9 (md, 2J(F4B
,
,
,
ꢂ148.7 (q (1:1:1:1), 1J(F, B) = 40 Hz, 3F, BF3).
F4A) = 300 Hz, 1F, F4B), ꢂ124.5 (ddddd, 3J(F5A, F4A) = 4 Hz, 3J(F5A
[Kꢄ18-crown-6][CF3CCl2–CF2BF3]. Anal. Calcd for C15H24BCl2F8
KO6 (573.15): C, 31.43; H, 4.22. Found: C, 32.6; H, 4.4.
F4B) = 8 Hz, 4J(F5A
,
F3A) = 12 Hz, 4J(F5A
,
F3B) = 20 Hz, 2J(F5A