A.J. Roche, B. Canturk / Journal of Fluorine Chemistry 126 (2005) 483–490
489
J = 159.4, 7.2 Hz), 125.49 (dd, J = 160.0, 9.0 Hz), 18.94 (q,
2
(80), 277 (40), 176 (100). HRMS (CI+) calculated for
C23H11F8N [M]+ 453.07638, found 453.0759.
J = 126.2 Hz); 19F NMR d ꢀ109.8 (d, J = 236.8 Hz, 1F),
ꢀ110.8(d, 2J = 236.8 Hz, 1F), ꢀ113.3 (d, 2J = 234.5 Hz, 1F),
ꢀ115.1(d, 2J = 234.5 Hz, 1F), ꢀ113.6 (d, 2J = 237.1 Hz, 1F),
ꢀ116.8(d, 2J = 237.1 Hz, 1F), ꢀ115.6 (d, 2J = 234.5 Hz, 1F),
ꢀ117.4 (d, 2J = 234.5 Hz, 1F); MS m/z 442 (M+, 40%), 176
(70), 256 (100). HRMS (CI+) calculated for C23H14F8 [M]+
442.09677, found 442.0957.
Method B using 4-cyanophenylboronic acid pinacol
ester gave 6 in 83% isolated yield; method C using
4-bromobenzonitrile gave 6 in 86%; method D using
4-bromobenzonitrile gave 6 in 76%.
4.3.5. 1,4-Bis(1,1,2,2,9,9,10,10-octafluoro[2.2]para-
cyclophan-4-yl)phenyl (12)
Method B using 2-methylphenylboronic acid pinacol
ester gave 5 in 78% isolated yield; method C using
2-bromotoluene gave 5 in 86%; method D using 2-
bromotoluene gave 5 in 79%.
Method A. Under a counter current of nitrogen gas, a round
bottomed flask was charged with 4-iodo-1,1,2,2,9,9,10,10-
octafluoro[2.2]paracyclophane (0.20 g, 0.42 mmol), pheny-
lene-1,4-diboronic acid (17 mg, 0.10 mmol), bis(triphenyl-
phosphine)palladium(II) chloride (7 mg, 0.01 mmol),
potassium carbonate (0.16 g, 1.16 mmol), THF (4 mL), and
water (1 mL). The vessel was thoroughly flushed with N2 and
refluxed for 48 h. The reaction mixture was then cooled to
room temperature, ether extracted (3 ꢂ 20 mL), dried
(MgSO4), and evaporated under reduced pressure. The crude
product was column chromatographed (hexane/chloroform 3/
1, Rf = 0.19) to give 1,4-bis(1,1,2,2,9,9,10,10-octafluor-
o[2.2]paracyclophan-4-yl)phenyl (40 mg, 51%); mp = 295–
296 8C. 1H NMR d 7.78 (s, 4H), 7.37–7.44 (m, 6H), 7.54–7.66
(m, 8H); 13C{1H} NMR d 133.41 (dd, J = 11.5, 6.0 Hz),
129.68, 129.60, 129.51, 129.46, 128.77 (dd. J = 7.2, 3.0 Hz),
128.46 (d, J = 7.4 Hz), 126.72 (t, J = 6.3 Hz) (aryl C–Hs);
118.53 (t, J = 265.3 Hz), 118.14 (t, J = 266.0 Hz), 117.89 (t,
J = 262.8 Hz), 117.50 (t, J = 261.1 Hz) (CF2s); 141.06 (d,
J = 6.9 Hz), 137.79 (quaternary); 135.07 (t, J = 25.4 Hz),
134.96 (t, J = 26.5 Hz), 134.65 (t, J = 26.5 Hz), 134.28 (t,
J = 26.5 Hz) (cyclophane Bridgeheads); relevant 13C{19F}
NMR data d 133.41 (d, J = 166.9 Hz), 128.77 (dd, J = 166.1,
6.2 Hz), 128.46(dd, J = 166.1, 6.5 Hz), 126.72(dd, J = 166.9,
6.8 Hz); 19F NMR d ꢀ101.0 (d, 2J = 239.0 Hz, 1F), ꢀ110.1
(d, 2J = 239.0 Hz, 1F), ꢀ114.4 (d, 2J = 234.5 Hz, 1F), ꢀ116.8
(d, 2J = 234.5 Hz, 1F), ꢀ114.4 (s, 2F), ꢀ115.7 (d, 2J =
4.3.3. 4-Phenyl-1,1,2,2,9,9,10,10-octafluo-
ro[2.2]paracyclophane (4)
Using the same scale and procedure as method A
with phenylboronic acid, after column chromatography
(hexane/dichloromethane 9/1, Rf = 0.30) gave 4-phenyl-
1
1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane (86%); H
NMR d 7.24 (s, 1H), 7.61–7.33 (m, 11H); 19F NMR d ꢀ102.1
(d, 2J = 239.9 Hz, 1F), ꢀ110.8 (d, 2J = 239.9 Hz, 1F),
ꢀ115.3 (m, 2F), ꢀ115.4 (d, 2J = 237.4 Hz, 1F), ꢀ117.9 (d,
2
2J = 237.4 Hz, 1F), ꢀ116.7 (d, J = 239.6 Hz, 1F), ꢀ117.8
(d, 2J = 239.6 Hz, 1F). Such characterization is in excellent
agreement with previously reported values [2].
Method B using phenylboronic acid pinacol ester gave 4
in 88% isolated yield; method C using bromobenzene gave 4
in 76%; method D using bromobenzene gave 4 in 81%.
4.3.4. 4-(4-Cyanophenyl)-1,1,2,2,9,9,10,10-
octafluoro[2.2]paracyclophane (6)
Using the same scale and procedure as method A with
4-cyanophenylboronic acid, after column chromatography
(hexane/ether 5/1, Rf = 0.28) gave 4-(4-cyanophenyl)-1,1,2,
2,9,9,10,10-octafluoro[2.2]paracyclophane (80%); mp =
1
3
4
160–162 8C. H NMR d 7.93 (dd, J = 9.0 Hz, J = 2.4 Hz,
2H), 7.87 (dd, J = 9.0 Hz, J = 2.4 Hz, 2H), 7.63 (d, J =
3
4
3
2
236.8 Hz, 1F), ꢀ116.8 (d, J = 236.8 Hz, 1F); MS m/z 778
9.0 Hz, 1H), 7.62 (d, 3J = 9.3 Hz, 1H), 7.55 (d, J = 6.9 Hz,
(M+, 60%), 127 (40), 176 (60), 602 (50), 601 (100); HRMS
(ESI) calculated for C38H18F16 [M + Na]+ 801.10507, found
801.1071.
3
1H), 7.53 (d, 3J = 7.5 Hz, 1H), 7.44 (d, 3J = 8.4 Hz, 2H), 7.33
(s, 1H); 13C{1H} NMR d 133.59 (dd, J = 10.0, 6.2 Hz),
131.21, 130.58, 129.63, 129.56, 129.48, 129.41, 128.90 (dd,
J = 5.6, 2.5 Hz), 126.88 (t, J = 6.0 Hz) (aryl C–Hs); 118.42
(t, J = 272.6 Hz), 118.27 (t, J = 273.2 Hz), 118.05 (t,
J = 270.1 Hz), 117.90 (t, J = 271.0 Hz) (CF2s); 134.37 (t,
J = 26.4 Hz), 134.14 (t, J = 26.8 Hz), 134.02 (t, J = 26.0 Hz),
133.88 (t, J = 26.1 Hz) (cyclophane bridgeheads); 141.58 (d,
J = 7.0 Hz), 137.39, 111.75 (quaternary); 117.42 (CN);
relevant 13C{19F} NMR data d 133.59 (d, J = 168.5 Hz),
131.21(dd, J = 167.6, 6.2 Hz), 130.58(dd, J = 164.6, 6.0 Hz),
129.63(dd, J = 168.8, 6.4 Hz), 129.56(dd, J = 168.3, 6.4 Hz),
129.48(dd, J = 165.9, 6.2 Hz), 129.41(dd, J = 168.3, 6.4 Hz),
128.90 (dd, J = 166.4, 6.2 Hz), 126.88 (dd, J = 167.8,
6.6 Hz); 19F NMR d ꢀ102.3 (d, 2J = 239.3 Hz, 1F),
Method B using phenylene-1,4-diboronic acid bis-
pinacol ester gave 12 in 60% isolated yield; method C
using 1,4-dibromobenzene gave 12 in 53%; method D using
1,4-dibromobenzene gave 12 in 56%.
4.3.6. 4,40-Bis(1,1,2,2,9,9,10,10-octafluoro[2.2]para-
cyclophan-4-yl)biphenyl (13)
Under a counter current of nitrogen gas, a round
bottomed flask was charged with 4-iodo-1,1,2,2,9,9,10,10-
octafluoro[2.2]paracyclophane (0.20 g, 0.42 mmol), pheny-
lene-1,4-diboronic acid (35 mg, 0.21 mmol), bis(triphenyl-
phosphine)palladium(II) chloride (7 mg, 0.01 mmol),
potassium carbonate (0.16 g, 1.16 mmol), THF (4 mL),
and water (1 mL). The vessel was thoroughly flushed with N2
and refluxed for 48 h. The reaction mixture was then cooled
to room temperature, ether extracted (3 ꢂ 20 mL), dried
2
2
ꢀ110.2 (d, J = 239.3 Hz, 1F), ꢀ114.5 (d, J = 232.0 Hz,
1F), ꢀ114.6 (s, 2F), ꢀ115.6 (d, 2J = 236.8 Hz, 1F), ꢀ116.9
(d, 2J = 236.8 Hz, 2F); MS m/z 453 (M+, 30%), 276 (74), 177