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DOI: 10.1055/s-2008-1078012
Efficient Conversion of Acetophenones into 1,3,5-Triarylbenzenes Catalyzed by Bismuth(III) Trifluoromethanesulfonate Tetrahydrate
Publication History
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
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References and Notes
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.
13The reaction was very slow in refluxing toluene (12 h, 17%).
14Cyclotrimerization 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.
15No 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]+.