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

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

• 1a Lindeman SV. Struchkov YuT. Michailov VN. Rusanov AL. Izv. Akad. Nauk. Ser. Khim.  1994,  1986 ; Chem. Abstr. 1995, 123, 32717p
• 1b Aslam M, and Aguilar DA. inventors; WO  9314065.  ; Chem. Abstr. 1993, 119, 270793x
• 1c Plater MJ. McKay M. Jackson T. J. Chem. Soc., Perkin Trans. 1  2000,  2695 
• 2a Kadota T. Kageyama H. Wakaya F. Gamo K. Shirota Y. Chem. Lett.  2004,  706 
• 2b Shirota Y. J. Mater. Chem.  2005,  15:  75 
• 2c Ikadai J. Yoshida H. Ohshita J. Kunai A. Chem. Lett.  2005,  34:  56 
• 3a Rebourt E. Pepin-Donat B. Dinh E. Polymer  1995,  36:  399 
• 3b Viallat A. Pepin-Donat B. Macromolecules  1997,  30:  4679 
• 3c Pepin-Donat B. de Geyer A. Viallat A. Polymer  1998,  39:  6673 
• 4 For a review, see: Wirth HO. Kern W. Schmitz E. Makromol. Chem.  1963,  68:  69 
• 5 Lyle RE. DeWitt EJ. Nichols NM. Cleland W. J. Am. Chem. Soc.  1953,  75:  5959 
• 6a Jin X. Xu F. Zhu Q. Ren X. Yan C. Wang L. Wang J. Synth. Commun.  2005,  35:  3167 
• 6b Jin X. Xu F. Zhu Q. Ren X. Li D. Yan C. Shi Y. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  2006,  45:  2781 
• 7a Elmorsy SS. Pelter A. Smith K. Tetrahedron Lett.  1991,  32:  4175 
• 7b Elmorsy SS. Pelter A. Smith K. Hursthouse MB. Ando D. Tetrahedron Lett.  1992,  33:  821 
• 7c Plater MJ. Praveen M. Tetrahedron Lett.  1997,  38:  1081 
• 8 Li Z. Sun W.-H. Jin X. Shao C. Synlett  2001,  1947 
• 9 Iranpoor N. Zeynizaded B. Synlett  1998,  1079 
• Dowex 50:
• 10a Lorette NB. J. Org. Chem.  1957,  22:  346 
• Nafion-H:
• 10b Yamato T. Hideshima C. Tashiro M. Prakash GKS. Olah GA. Catal. Lett.  1990,  6:  341 
• 10c Yamata T. Hideshima C. Nagano Y. Tashiro M. J. Chem. Res., Synop.  1996,  266 
• For reviews on bismuth(III) trifluoromethanesulfonate, see:
• 11a Antoniotti S. Synlett  2003,  1566 
• 11b Gaspard-Iloughmane H. Le Roux C. Eur. J. Org. Chem.  2004,  2517 
• For recent leading references, see:
• 11c Kamal A. Ahmed SK. Sandbhor M. Khan MNA. Arifuddin M. Chem. Lett.  2005,  1142 
• 11d Anderson ED. Ernat JJ. Nguyen MP. Palma AC. Mohan RS. Tetrahedron Lett.  2005,  46:  7747 
• 11e Lacey JR. Anzalone PW. Duncan CM. Hackert MJ. Mohan RS. Tetrahedron Lett.  2005,  46:  8507 
• 11f Ollevier T. Li Z. Org. Biomol. Chem.  2006,  4:  4440 
• 11g Ollevier T. Nadeau E. Synlett  2006,  219 
• 11h Adinolfi M. Iadonisi A. Ravida A. Valerio S. Tetrahedron Lett.  2006,  47:  2595 
• 11i Ollevier T. Mwene-Mbeja TM. Tetrahedron Lett.  2006,  47:  4051 
• 11j Callens E. Burton AJ. Barrett AGM. Tetrahedron Lett.  2006,  47:  8699 
• 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 

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

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]⁺.