The Journal of Organic Chemistry
Article
2865, 2219, 1583, 1510, 1463, 1451, 1350, 1085, 758, 734, 628; UV−
vis λmax/nm (THF) (log ε) 451 (3.78), 427 (3.41), 420 (3.56), 383
(3.69), 353 (3.95), 331 (4.48), 318 (sh, 4.25), 280 (3.94), 251 (3.94);
HRMS (APPI-TOF) calcd for C44H44 572.3443, found: 572.3415.
Synthesis of 5,6,11,12-Tetrakis(phenylethynyl)dibenzo[b,h]-
biphenylene (5b). Compound 5b was synthesized following the
same procedure as 5c (0.25 g, yield = 45%): mp >400 °C (darkens 315
°C); 1H NMR (500 MHz, CDBr3) δ 8.26−8.21 (m, 4H, ArH), 7.52−
7.46 (m, 4H, ArH), 7.40−7.34 (m, 8H, ArH), 7.24−7.19 (m, 4H),
7.13−7.06 (m, 8H, ArH); 13C NMR (125 MHz, CDBr3) δ 145.1,
133.7, 130.6, 127.2, 126.5, 126.1, 121.5, 110.6, 98.6, 83.7; IR (ATR)
(cm−1) 3053, 1485, 1439, 1362, 1125, 1065, 1022, 913, 752, 688, 629;
UV−vis λmax/nm (THF) (log ε) 464 (4.29), 432 (4.27), 353 (4.91),
308 (4.86), 277 (5.45), 252 (4.80); HRMS (APPI-TOF) calcd for
C52H28 652.2191, found: 652.2170.
Cyclotrimerization Using Rh(I) or Ni(0) Catalyst. In an oven-
dried microwave tube were added 5d (15 mg, 0.04 mmol), 3-hexyne
(0.05 mL, 0.04 mmol), and chloro(1,5-cyclooctadiene)rhodium(I)
dimer (0.002 g, 0.005 mmol) or bis(triphenylphosphine)-
dicarbonylnickel (0) (0.003 mg, 0.005 mmol). Toluene (5 mL) was
added to the microwave tube, and it was closed under nitrogen. The
reaction mixture was irradiated (150 °C, 250 W) using CEM Discover
(model no. 908005) microwave reactor for 30 min. The reaction was
monitored by mass spectrometry (APPI-MS).
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ASSOCIATED CONTENT
* Supporting Information
■
S
Crystallographic information files for 5a−c, 7c, 9, and 10 (CIF)
and NMR, IR, UV−vis, and mass spectra. This material is
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AUTHOR INFORMATION
Corresponding Author
Notes
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The authors declare no competing financial interest.
(37) Suresh, V.; Selvam, J. P.; Rajesh, K.; Shekhar, V.; Babu, D. C.;
Venkateswarlu, Y. Synthesis 2010, 11, 1763−1765.
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ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
(CHE-0957702).
■
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