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Synlett 2008(15): 2365-2367  
DOI: 10.1055/s-2008-1078012
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Conversion of Acetophenones into 1,3,5-Triarylbenzenes Catalyzed by Bismuth(III) Trifluoromethanesulfonate Tetrahydrate

Fumiaki Ono, Yuichi Ishikura, Yuusuke Tada, Masato Endo, Tsuneo Sato*
Department of Life Science, Kurashiki University of Science and the Arts, Kurashiki 712-8505, Japan
Fax: +81(86)4401062; e-Mail: sato@chem.kusa.ac.jp;
Further Information

Publication History

Received 14 April 2008
Publication Date:
31 July 2008 (online)

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Abstract

Bismuth(III) trifluoromethanesulfonate tetrahydrate is found to efficiently catalyze the cyclotrimerization of acetophenones into 1,3,5-triarylbenzenes in good yields.

Key words

bismuth(III) trifluoromethanesulfonate - catalysis - ketones - Lewis acids - 1,3,5-triarylbenzenes

    References and Notes

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12

To the best of our knowledge, there are only two successful reports4,7c on the use of this type of compound in the cyclotrimerization process.

13

The reaction was very slow in refluxing toluene (12 h, 17%).

14

Cyclotrimerization of 2-methylacetophenone by the Wirth method [dry HCl(excess), (EtO)3CH (1.2 equiv), EtOH, r.t., 24 h]4 and the Elmorsy method [SiCl4 (1.0 equiv), EtOH, Δ, 24 h]7c gave the product in 26% and 32% yields, respectively.

15

No desired product was obtained by Nafion-H-catalyzed cyclotrimerization of 2,5-dimethylacetophenone.¹0b

17

Selected Physical and Spectroscopic Data
1,3,5-Triphenylbenzene
Mp 174.1-174.7 ˚C (Lit.4 175-176 ˚C). MS (EI): m/z = 306 [M]+.
1,3,5-Tris(4-methylphenyl)benzene
Mp 175.7-176.9 ˚C (Lit.5 178 ˚C). MS (EI): m/z = 348 [M]+.
1,3,5-Tris[4-(methylethyl)phenyl]benzene
Mp 167.5-168.1 ˚C (Lit.5 166 ˚C). MS (EI): m/z = 432 [M]+.
1,3,5-Tris(4-phenylphenyl)benzene
Mp 236.2-238.0 ˚C (Lit.4 241 ˚C). MS (EI): m/z = 534 [M]+.
1,3,5-Tris(4-fluorophenyl)benzene
Mp 236.5-238.0 ˚C (Lit.5 238 ˚C). ¹H NMR (500 MHz, CDCl3): δ = 7.17 (t-like, J = 8.6 Hz, 6 H), 7.61-7.65 (m, 6 H), 7.66 (s, 3 H). ¹³C NMR (125 MHz, CDCl3): δ = 115.8 (d, J = 21.6 Hz), 124.8, 128.9 (d, J = 8.3 Hz), 137.0 (d, J = 4.1 Hz), 141.5, 162.7 (d, J = 245.8 Hz). MS (EI): m/z = 360 [M]+.
1,3,5-Tris(4-chlorophenyl)benzene
Mp 244.1-244.9 ˚C (Lit.5 246 ˚C). MS (EI): m/z = 408 [M]+.
1,3,5-Tris(4-bromophenyl)benzene
Mp 260.2-260.9 ˚C (Lit.5 262 ˚C). MS (EI): m/z 539 [M]+.
1,3,5-Tris(4-iodophenyl)benzene
Mp 264.6-265.9 ˚C (Lit.5 265 ˚C). MS (EI): m/z = 683 [M]+.
1,3,5-Tris(3-methylphenyl)benzene
Mp 116.8-118.1 ˚C (Lit.4 118 ˚C).¹H NMR (500 MHz, CDCl3): δ = 2.45 (s, 9 H), 7.21 (d, J = 7.7 Hz, 3 H), 7.37 (t, J = 7.7 Hz, 3 H), 7.50 (d, J = 7.7 Hz, 3 H), 7.51 (s, 3 H), 7.75 (s, 3 H). ¹³C NMR (125 MHz, CDCl3): δ = 21.6, 124.4, 125.1, 128.1, 128.2, 128.7, 138.4, 141.2, 142.3. MS (EI): m/z = 348 [M]+.
1,3,5-Tris(3-chlorophenyl)benzene
Mp 172.4-173.0 ˚C (Lit.5 171 ˚C). MS (EI): m/z = 408 [M]+.
1,3,5-Tris(2-methylphenyl)benzene
Mp 135.6-135.8 ˚C (Lit.4 134-135 ˚C). ¹H NMR (500 MHz, CDCl3): δ = 2.37 (s, 9 H), 7.22-7.34 (m, 15 H). ¹³C NMR (125 MHz, CDCl3): δ = 20.6, 125.8, 127.3, 128.5, 129.9, 130.4, 135.4, 141.5, 141.7. MS (EI): m/z = 348 [M]+.
1,3,5-Tris(2-chlorophenyl)benzene
Mp 165.1-165.5 ˚C. ¹H NMR (500 MHz, CDCl3): δ = 7.28-7.36 (m, 6 H), 7.45-7.52 (m, 6 H), 7.58 (s, 3 H). ¹³C NMR (125 MHz, CDCl3): δ = 126.9, 128.7, 129.8, 130.1, 131.6, 132.6, 138.9, 139.9. MS (EI): m/z = 408 [M]+. HRMS (EI): m/z calcd for C24H15Cl3: 408.0242; found: 408.0236.
1,3,5-Tris(2,5-dimethylphenyl)benzene
Mp 148.3-149.4 ˚C (Lit.4 149 ˚C). ¹H NMR (500 MHz, CDCl3): δ = 2.32 (s, 9 H), 2.35 (s, 9 H), 7.08 (d, J = 8.0 Hz, 3 H), 7.15 (s, 3 H), 7.17 (d, J = 8.0 Hz, 3 H), 7.26 (s, 3 H). ¹³C NMR (125 MHz, CDCl3): δ = 20.2, 20.9, 127.9, 128.4, 130.3, 130.6, 132.2, 135.2, 141.5, 141.6. MS (EI): m/z = 390 [M]+.