Beilstein J. Org. Chem. 2013, 9, 698–704.
6H), 2.04–1.96 (m, 18H), 1.25 (s, 6H); 13C NMR (100 MHz, 270 Hz); HRMS (ESI–QTOF): m/z calcd for C60H31F18
CDCl3) δ 181.5, 162.8, 143.7, 140.9, 140.7, 139.6, 139.39, 1093.2138, found 1093.2100.
139.3, 138.8, 138.7, 135.8, 135.7, 135.2, 135.0, 130.0, 129.4,
129.0, 128.7, 128.2, 36.4, 35.8, 35.7, 23.3, 21.5, 21.48, 21.43, 4,7,12,15-Tetrakis(4-trifluoromethylphenyl)[2.2]paracyclo-
21.0, 20.0, 18.8, 17.4; ESIMS: m/z 863 along with the expected phane (28): Prepared from 4,7,12,15-tetrabromo[2.2]paracyclo-
isotope peaks. HRMS (ESI–QTOF): m/z calcd for phane (26, 100 mg, 0.19 mmol), complex 1 (3 mg, 2 mol %),
C46H56N6O4Pd 863.3476, found 863.3491.
4-trifluoromethylphenylboronic acid (8, 174 mg, 0.92 mmol),
NaOH (61 mg, 1.53 mmol), PPh3 (2 mg, 4 mol %). Yield
132 mg, 88%; colorless solid, mp 224 °C. 1H NMR (500 MHz,
CDCl3) δ 7.69–7.67 (m, 8H), 7.49–7.47 (m, 8H), 6.86 (s, 4H);
3.52 and 2.83 (AA’BB’ pattern, 8H); 13C NMR (125 MHz,
CDCl3) δ 143.7, 139.5, 137.5, 132.6, 129.4 (q, J = 32.6 Hz),
129.2, 124.3 (q, J = 270 Hz), 33.4; HRMS (ESI–QTOF): m/z
calcd for C44H29F12 785.2078, found 785.2077.
Representative procedures for
Suzuki–Miyaura coupling of polybromo-
arenes:
Synthesis of 1,3,6,8-tetraphenylpyrene (19): A mixture of
1,3,6,8-tetrabromopyrene (18, 100 mg, 0.193 mmol), phenyl-
boronic acid (5, 113 mg, 0.93 mmol, 4.8 equiv), complex 1
(3 mg, 2 mol %), triphenylphosphine (4 mg, 4 mol %), NaOH
(62 mg, 1.54 mmol, 8 equiv) was heated under reflux in 4 mL
of 1,4-dioxane under nitrogen atmosphere. The reaction was
completed in 8 h (monitored by TLC). The reaction mixture
was diluted with water (10 mL) and extracted with CH2Cl2 (3 ×
5 mL). The organic layer was dried over sodium sulfate and
filtered, and then the solvent was removed under vacuum. The
crude product was recrystallized from CH2Cl2 to give 1,3,6,8-
tetraphenylpyrene (19, 95 mg, 0.19 mmol) in 97% yield as a
lime-yellow solid, mp: 264 °C. 1H NMR (400 MHz, CDCl3) δ
8.17 (s, 4H), 8.01 (s, 2H), 7.68–7.66 (m, 8H), 7.55–7.52 (m,
8H), 7.48–7.44 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 141.2,
137.4, 130.8, 129.6, 128.5, 128.2, 127.4, 126.1, 125.4; HRMS
(ESI–QTOF): m/z calcd for C40H27 507.2113, found 507.2094.
Supporting Information
Supporting Information File 1
Spectroscopic characterization data of compounds 8, 10,
11, 13, 15, 17, 22, 24 and 27.
Supporting Information File 2
CIF file for complex 1.
Supporting Information File 3
CIF file for complex 2.
1,3,6,8-Tetrakis(4-trifluoromethylphenyl)pyrene (20):
Prepared from 1,3,6,8-tetrabromopyrene (18, 100 mg,
0.19 mmol), complex 1 (3 mg, 2 mol %), 4-trifluo-
romethylphenylboronic acid (8, 176 mg, 0.93 mmol), NaOH
(62 mg, 1.54 mmol), PPh3 (2 mg, 4 mol %). Yield 142 mg,
94%; colorless solid, mp 231–232 °C (lit. 231 °C) [32]. Acknowledgements
1H NMR (500 MHz, CDCl3) δ 8.13 (s, 4H), 7.99 (s, 2H), We thank CSIR and DST, New Delhi for financial support, the
7.83–7.77 (AA’BB’ pattern, 16H); 13C NMR (125 MHz, Department of Chemistry, and SAIF, IIT Madras for infrastruc-
CDCl3) δ 144.3, 136.4, 131.0, 130.0 (q, J = 31.8 Hz), 129.4, ture. JBS thanks CSIR for a fellowship.
128.5, 125.9, 125.7, 125.6 (q, J = 2.5 Hz), 124.4 (q, J =
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779.1608, found 779.1616.
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