Download PDF
Synlett 2014; 25(17): 2493-2497
DOI: 10.1055/s-0034-1378650
letter
© Georg Thieme Verlag Stuttgart · New York

Activation of the C–C Bond Using Brønsted Acid NaHSO4/SiO2: Synthesis of Triarylmethanes from 3-Benzhydryl Pentane-2,4-dione and Aromatic Compounds

Tadashi Aoyama*
a   Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan   Fax: +81(3)32590818   Email: aoyama.tadashi@nihon-u.ac.jp
b   The Center for Creative Materials Research, Research Institute of Science and Technology, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan
,
Mamiko Hayakawa
a   Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan   Fax: +81(3)32590818   Email: aoyama.tadashi@nihon-u.ac.jp
,
Sumire Ogawa
a   Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan   Fax: +81(3)32590818   Email: aoyama.tadashi@nihon-u.ac.jp
,
Erika Nakajima
a   Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan   Fax: +81(3)32590818   Email: aoyama.tadashi@nihon-u.ac.jp
,
Emi Mitsuyama
a   Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan   Fax: +81(3)32590818   Email: aoyama.tadashi@nihon-u.ac.jp
,
Taku Iwabuchi
a   Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan   Fax: +81(3)32590818   Email: aoyama.tadashi@nihon-u.ac.jp
,
Toshio Takido
a   Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan   Fax: +81(3)32590818   Email: aoyama.tadashi@nihon-u.ac.jp
,
Mitsuo Kodomari
c   The Institute of Natural Sciences, College of Humanities and Science, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan
› Author Affiliations
Further Information

Publication History

Received: 04 July 2014

Accepted after revision: 22 July 2014

Publication Date:
25 August 2014 (online)

    Permissions and Reprints All articles of this category


Abstract

A novel and efficient method for the activation of the C(sp3)–C(sp3) bond was developed. The C(sp3)–C(sp3) bond in 3-benzhydryl pentane-2,4-dione was easily cleaved in the presence of NaHSO4/SiO2 to form benzhydryl cation which reacted with aromatic compounds at 110 °C for five to six hours to afford triarylmethanes in good yields. This reaction using Brønsted acids was applicable for the alkylation of electron-rich aromatics containing alkyl halides as a side chain.

Key words

C–C bond activation - C–C bond formation - solid acid - alkylation - heterogeneous reaction

Supporting Information

    for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
  • Supporting Information
 

  • References and Notes

    • 1a Yamamoto Y, Itonaga K. Chem. Eur. J. 2008; 14: 10705
      Crossref
    • 1b Wang F, Ueda W. Chem. Eur. J. 2009; 15: 742
      CrossrefPubMed
    • 1c McCubbin JA, Krokhin OV. Tetrahedron Lett. 2010; 51: 2447
      Crossref
    • 1d Roy S, Podder S, Choudhury J. J. Chem. Sci. 2008; 120: 429
      Crossref
    • 1e Sun H, Li B, Chen S, Li J, Hua R. Tetrahedron 2007; 63: 10185
      Crossref
    • 1f Sanz R, Martinez A, Miguel D, Alvarez-Guiterrez JM, Rodriguez F. Adv. Synth. Catal. 2006; 348: 1841
      Crossref
    • 1g Bras JL, Muzart J. Tetrahedron 2007; 63: 7942
      Crossref
    • 1h Thirupathi P, Kim SS. Tetrahedron 2010; 66: 2995
      Crossref
    • 1i Niggemann M, Meel MJ. Angew. Chem. Int. Ed. 2010; 49: 3684
      CrossrefPubMed
    • 1j Sun G, Wang Z. Tetrahedron Lett. 2008; 49: 4929
      Crossref
    • 1k Sato Y, Aoyama T, Takido T, Kodomari M. Tetrahedron 2011; 68: 7077
    • 2a Seiser T, Cramer N. J. Am. Chem. Soc. 2010; 132: 5340
      Crossref
    • 2b Winter C, Krause N. Angew. Chem. Int. Ed. 2009; 48: 2460
      Crossref
    • 2c Murakami M, Makino M, Ashida S, Matsuda T. Bull. Chem. Soc. Jpn. 2006; 79: 1315
      Crossref
    • 2d Pohlhaus PD, Bowman RK, Johnson JS. J. Am. Chem. Soc. 2004; 126: 2294
      CrossrefPubMed
    • 2e Matsumura S, Maeda Y, Nishimura T, Uemura S. J. Am. Chem. Soc. 2003; 125: 8862
      CrossrefPubMed
    • 2f Bart SC, Chirik PJ. J. Am. Chem. Soc. 2003; 125: 886
      Crossref
    • 2g Perthuisot C, Edelbach BL, Zubris DL, Simhai N, Iverson CN, Müller C, Satoh T, Jones WD. J. Mol. Catal. A: Chem. 2002; 189: 157
      Crossref
    • 2h Kondo T, Kaneko Y, Taguchi Y, Nakamura A, Okada T, Shiotsuki M, Ura Y, Wada K, Mitsudo T. J. Am. Chem. Soc. 2002; 124: 6824
      Crossref
    • 2i Kim S, Takeuchi D, Osakada K. J. Am. Chem. Soc. 2002; 124: 762
      Crossref
    • 3a Park YJ, Park J.-W, Jun C.-H. Acc. Chem. Res. 2008; 41: 222
      CrossrefPubMed
    • 3b Jun C.-H, Moon CW, Lee D.-Y. Chem. Eur. J. 2002; 8: 2422
      Crossref
    • 3c Lee D.-Y, Kim I.-J, Jun C.-H. Angew. Chem. Int. Ed. 2002; 41: 3031
      Crossref
    • 3d Jun C.-H, Lee H, Lim S.-G. J. Am. Chem. Soc. 2001; 123: 751
      Crossref
    • 3e Jun C.-H, Lee D.-Y, Kim Y.-H, Lee H. Organometallics 2001; 20: 2928
      Crossref
    • 3f Jun C.-H, Lee D.-Y, Lee H, Hong J.-B. Angew. Chem. Int. Ed. 2000; 39: 3070
      Crossref
    • 3g Gandelman M, Milstein D. Chem. Commun. 2000; 1603
    • 4a Sugiishi T, Kimura A, Nakamura H. J. Am. Chem. Soc. 2010; 132: 5332
      CrossrefPubMed
    • 4b He C, Guo S, Huang L, Lei A. J. Am. Chem. Soc. 2010; 132: 8273
      Crossref
    • 4c Nájera C, Sansano JM. Angew. Chem. Int. Ed. 2009; 48: 2452
      Crossref
    • 4d Schmink JR, Leadbeater NE. Org. Lett. 2009; 11: 2575
      CrossrefPubMed
    • 4e Tobisu M, Chatani N. Chem. Soc. Rev. 2008; 37: 300
      Crossref
    • 4f Kuninobu Y, Takata H, Kawata A, Takai K. Org. Lett. 2008; 10: 3133
      Crossref
    • 5a Xu Q, Cheng B, Ye X, Zhai H. Org. Lett. 2009; 11: 4136
      Crossref
    • 5b Takahashi T, Song Z, Hsieh YF, Nakajima K, Kanno K. J. Am. Chem. Soc. 2008; 130: 15236
      Crossref
  • 6 Aoyama T, Sho K, Takido T, Kodomari M. Chem. Lett. 2011; 40: 484
    Crossref
    • 7a Li H, Li W, Liu W, He Z, Li Z. Angew. Chem. Int. Ed. 2011; 50: 2975
      Crossref
    • 7b Li W, Zheng X, Li Z. Adv. Synth. Catal. 2013; 355: 181
      Crossref
    • 8a Sattler A, Parkin G. Nature (London, U.K.) 2010; 463: 523
      Crossref
    • 8b Cicchillo RM, Zhang H, Blodgett JA. V, Whitteck JT, Li G, Nair SK, van der Donk WA, Metcalf WW. Nature (London, U.K.) 2009; 459: 871
      Crossref
    • 8c Horino Y. Angew. Chem. Int. Ed. 2007; 46: 2144
      Crossref
  • 9 Aoyama T, Takido T, Kodomari M. Synlett 2004; 2307
    Article in Thieme Connect
  • 10 Aoyama T, Suzuki T, Takido T, Kodomari M. Synth. Commun. 2013; 43: 553
  • 11 Melting points were determined on Büchi Melting Point B-540. NMR spectra were recorded on a JEOL ECX 400 spectrometer. Tetramethylsilane (δ = 0 ppm) was used as an internal standard for 1H NMR and CDCl3 (δ = 77.0 ppm) for 13C NMR spectroscopy. MS analyses were performed on a SHIMAZU GCMS-QP2010 or on a JMS-GCmate (JEOL). Elemental analyses were performed on a J Science Lab. micro corder JM-10. Preparation of NaHSO4/SiO2 SiO2 [Wakogel C-200 (Wako Pure Chemical Ind. Ltd.), 10 g] was added to a solution of NaHSO4·H2O (30 mmol, 4.14 g) in distilled H2O, and the mixture was stirred at r.t. for 0.5 h. H2O was removed by rotary evaporator under reduced pressure, and the resulting reagent was dried in vacuo (1.33 mbar) at 120 °C for 5 h. Typical Procedure A mixture of diketones 1 (1.0 mmol), aromatics 2 (3.0 mmol), and NaHSO4/SiO2 (2.1 mmol/g, 1.00 g) in chlorobenzene (5 mL) was stirred at 110 °C for 6 h, and then the used supported reagent was removed by filtration. The filtrate was evaporated to leave crude product, which was purified by glass tube oven and column chromatography (hexane–EtOAc) to obtain 3. 2-Benzhydryl-4-chlorophenol (3an) Oil. 1H NMR (400 MHz, CDCl3): δ = 4.78 (s, 1 H), 5.67 (s, 1 H), 6.68 (dd, J = 7.1, 2.5 Hz, 1 H), 6.77 (d, J = 2.5 Hz, 1 H), 7.06–7.12 (m, 5 H), 7.21–7.32 (m, 6 H). 13C NMR (100 MHz, CDCl3): δ = 50.73, 117.3, 125.7, 126.9, 127.7, 128.7, 129.2, 130.2, 132.2, 141.6, 152.0. HRMS (EI): m/z [M+] calcd for C19H15OCl: 294.0811; found: 294.0809. 2-Benzhydryl-4-nitrophenol (3ao) Yellow solid; mp 254–257 °C (hexane). 1H NMR (400 MHz, CDCl3): δ = 5.75 (s, 1 H), 6.89 (d, J = 8.9, 1 H), 7.12–7.14 (m, 4 H), 7.27–7.37 (m, 7 H), 7.77 (d, J = 2.8 Hz, 1 H), 8.07 (dd, J = 8.9, 2.8 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 50.6, 116.1, 124.4, 126.5, 127.3, 128.9, 129.2, 131.5, 141.0, 141.7, 159.2. HRMS (EI): m/z [M+] calcd for C19H15NO3: 305.1052; found: 305.1054. Anal. Calcd for C19H15NO3: C, 74.74; H, 4.95; N, 4.59. Found: C, 74.89; H, 4.83; N, 4.51. 1-(4-Methoxyphenylethyl)-3,4-dimethoxybenzene (3ch) Colorless oil. 1H NMR (400 MHz, CDCl3): δ = 1.59 (d, J = 6.8 Hz, 3 H), 3.78 (s, 3 H), 3.82 (s, 3 H), 3.85 (s, 3 H), 4.05 (q, J = 6.8 Hz, 1 H), 6.70 (d, J = 1.8 Hz, 1 H), 6.75–6.85 (m, 4 H), 7.11–7.14 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 22.3, 43.5, 55.2, 55.8, 55.8, 110.9, 111.0, 113.7, 119.1, 128.4, 138.8, 139.4, 147.2, 148.7, 157.7. HRMS (EI): m/z [M+] calcd for C17H20O3: 272.1412; found: 272.1413. 1-(4-Methoxybenzhydryl)-3,4-dimethoxybenzene (3gh) Colorless oil. 1H NMR (400 MHz, CDCl3): δ = 3.75 (s, 3 H), 3.78 (s, 3 H), 3.84 (s, 3 H), 5.45 (s, 1 H), 6.59 (dd, J = 8.2, 2.0 Hz, 1 H), 6.66 (d, J = 2.0 Hz, 1 H), 6.77 (d, J = 8.2 Hz, 1 H), 6.80–6.84 (m, 2 H), 7.00–7.01 (m, 2 H), 7.10–7.12 (m, 2 H), 7.17–7.30 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 55.2, 55.5, 55.7, 55.8, 110.7, 112.6, 113.6, 121.3, 126.1, 128.2, 129.2, 130.2, 136.2, 136.8, 144.4, 147.3, 148.6, 157.9. HRMS (EI): m/z [M+] calcd for C22H22O3: 334.1569; found: 334.1568. 2-Benzhydryl-4-(2-chloroethyl)phenol (3as) Oil. 1H NMR (400 MHz, CDCl3): δ = 2.88 (t, J = 7.6 Hz, 2 H), 3.56 (t, J = 7.6 Hz, 2 H), 4.61 (s, 1 H), 5.71 (s, 1 H), 6.64 (d, J = 2.3 Hz, 1 H), 6.73 (d, J = 8.2 Hz, 1 H), 6.98 (dd, J = 8.2, 2.3 Hz, 1 H), 7.10–7.13 (m, 4 H), 7.22–7.32 (m, 6 H). 13C NMR (100 MHz, CDCl3): δ = 38.4, 45.3, 50.8, 116.2, 126.7, 128.1, 128.6, 129.3, 130.3, 130.5, 130.8, 142.3, 152.3. HRMS (EI): m/z [M+] calcd for C21H19OCl: 322.1124; found: 322.1126. 2-Benzhydryl-4-(2-bromoethyl)phenol (3at) Oil. 1H NMR (400 MHz, CDCl3): δ = 2.96 (t, J = 7.8 Hz, 2 H), 3.41 (t, J = 7.8 Hz, 2 H), 4.70 (s, 1 H), 5.71 (s, 1 H), 6.63 (d, J = 1.8 Hz, 1 H), 6.71 (d, J = 8.0 Hz, 1 H), 6.96 (dd, J = 8.0, 1.8 Hz, 1 H), 7.12 (d, J = 7.3 Hz, 4 H), 7.21–7.31 (m, 6 H). 13C NMR (100 MHz, CDCl3): δ = 33.5, 38.6, 50.7, 116.2, 126.7, 128.0, 128.5, 129.3, 130.5, 130.7, 131.2, 142.3, 152.3. HRMS (EI): m/z [M+] calcd for C21H19OBr: 366.0619; found: 366.0618. 2-Benzhydryl-4-(2-bromopropyl)phenol (3au) White solid; mp 88–91 °C (hexane). 1H NMR (400 MHz, CDCl3): δ = 1.59 (d, J = 6.4 Hz, 3 H), 2.90 (dd, J = 14.2, 7.0 Hz, 1 H), 3.05 (dd, J = 14.2, 7.0 Hz, 1 H), 3.70 (s, 3 H), 4.10–4.19 (m, 1 H), 5.91 (s, 1 H), 6.67 (d, J = 2.3 Hz, 1 H), 6.81 (d, J = 8.2 Hz, 1 H), 7.04 (dd, J = 8.2, 2.3 Hz, 1 H), 7.07–7.10 (m, 4 H), 7.17–7.28 (m, 7 H). 13C NMR (100 MHz, CDCl3): δ = 25.4, 46.6, 49.4, 51.4, 55.6, 110.5, 126.0, 128.1, 29.4, 130.1, 131.3, 132.6, 143.7, 143.8, 156.0. HRMS (EI): m/z [M+] calcd for C23H23OBr: 394.0932; found: 394.0932. Anal. Calcd for C23H23BrO: C, 69.88; H, 5.86. Found: C, 69.75; H, 5.70.