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

doi:10.1055/s-2008-1078012

LETTER

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;

Abstract

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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

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References

References and Notes

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Nafion-H:

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12

To the best of our knowledge, there are only two successful reports^4,7c 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

16 Bismuth(III) trifluoromethanesulfonate tetrahydrate was prepared according to the method described in the literature: Labrouillere M. Le Roux C. Gaspard H. Laporterie A. Dubac J. Tetrahedron Lett. 1999, 40: 285

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]⁺.