One-Pot Synthesis of Benzo[b]thiophenes and Naphtho[2,1-b]thiophenes in the Presence of Acidic and Basic Supported Reagents

Tadashi Aoyama; Toshio Takido; Mitsuo Kodomari

doi:10.1055/s-2005-918928

LETTER

One-Pot Synthesis of Benzo[b]thiophenes and Naphtho[2,1-b]thiophenes in the Presence of Acidic and Basic Supported Reagents

Tadashi Aoyama*^a, Toshio Takido^a, Mitsuo Kodomari^b
^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; e-Mail: aoyama@chem.cst.nihon-u.ac.jp;
^b Department of Applied Chemistry, Shibaura Institute of Technology, Shibaura, Minato-ku, Tokyo 108-8548, Japan

Abstract

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Abstract

A simple and efficient method has been developed for the synthesis of benzo[b]thiophenes and naphtho[2,1-b]thiophenes from aryl thiols and α-halo ketones by using an acid- and a base-supported reagent system, Na₂CO₃/SiO₂-PPA/SiO₂. Reaction of α-halo ketones with aryl thiols is promoted by Na₂CO₃/SiO₂ to afford α-phenylthio ketones, which cyclizes in the presence of PPA/SiO₂ to give the corresponding arylthiophenes in one-pot.

Key words

one-pot synthesis - benzo[b]thiophenes - naphtho[2,1-b]thiophenes - supported reagents

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References

<A NAME="RU25005ST-1A">1a</A> Kodomari M. Nawa S. Miyoshi T. J. Chem. Soc., Chem. Commun. 1995, 1895

<A NAME="RU25005ST-1B">1b</A> Suzuki Y. Kodomari M. Chem. Lett. 1998, 1091

<A NAME="RU25005ST-1C">1c</A> Kodomari M. Aoyama T. Suzuki Y. Tetrahedron Lett. 2002, 43: 1717

<A NAME="RU25005ST-1D">1d</A> Aoyama T. Takido T. Kodomari M. Tetrahedron Lett. 2004, 45: 1873

<A NAME="RU25005ST-1E">1e</A> Aoyama T. Murata S. Nagata S. Takido T. Kodomari M. Tetrahedron Lett. 2005, 46: 4875

<A NAME="RU25005ST-2A">2a</A> Francisco MA. Kurs A. Katritzky AR. Rasala D. J. Org. Chem. 1998, 53: 596

<A NAME="RU25005ST-2B">2b</A> Pinney KG. Bounds AD. Dingeman KM. Mocharla VP. Pettit GR. Bai R. Hamel E. Bioorg. Med. Chem. Lett. 1999, 9: 1081

<A NAME="RU25005ST-2C">2c</A> Kim S. Yang J. DiNinno F. Tetrahedron Lett. 1999, 40: 2909

<A NAME="RU25005ST-2D">2d</A> Queiroz M.-JRP. Dubest R. Aubard J. Faure R. Guglielmetti R. Dyes Pigm. 2000, 47: 219

<A NAME="RU25005ST-2E">2e</A> Qiao JX. Cheng X. Modi DP. Rossi KA. Luettgen JM. Knabb RM. Jadhav PK. Wexler RR. Bioorg. Med. Chem. Lett. 2005, 15: 29

<A NAME="RU25005ST-3A">3a</A> Tércio J. Ferreira B. Catani V. Comasseto JV. Synthesis 1987, 149

<A NAME="RU25005ST-3B">3b</A> Wei-Yuan H. Yan-Song L. Heteroat. Chem. 1995, 6: 287

<A NAME="RU25005ST-4A">4a</A> Nanteuil GD. Lila-Ambroise C. Rupin A. Vallez M.-O. Verbeuren TJ. Bioorg. Med. Chem. Lett. 2003, 13: 1705

<A NAME="RU25005ST-4B">4b</A> Takeuchi K. Kohn TJ. Sall DJ. Denney ML. McCowan JR. Smith GF. Gifford-Moore DS. Bioorg. Med. Chem. Lett. 1999, 9: 759

<A NAME="RU25005ST-4C">4c</A> Pinny KG. Bounds AD. Dubgenab KM. Mocharla VP. Pettit GR. Bai R. Hamel E. Bioorg. Med. Chem. Lett. 1999, 9: 1081

<A NAME="RU25005ST-4D">4d</A> Graham SL. Shepard KL. Anderson PS. Baldwin JJ. Best DB. Christy ME. Freedman MB. Gautheron P. Habecker CN. Hoffman JM. J. Med. Chem. 1989, 32: 2548

<A NAME="RU25005ST-5A">5a</A> Benincori T. Gladiali S. Rizzo S. Sannicolò F. J. Org. Chem. 2001, 66: 5940

<A NAME="RU25005ST-5B">5b</A> Sannicolò F. Benincori T. Rizzo S. Gladiali S. Pulacchini S. Zotti G. Synthesis 2001, 2327

<A NAME="RU25005ST-6A">6a</A> Ichikawa J. Wada Y. Okauchi T. Minami T. Chem. Commun. 1997, 1537

<A NAME="RU25005ST-6B">6b</A> Ichikawa J. Wada Y. Fujiwara M. Sakoda K. Synthesis 2002, 1917

<A NAME="RU25005ST-7A">7a</A> Mukherjee C. De A. Synlett 2002, 325

<A NAME="RU25005ST-7B">7b</A> Mukherjee C. Kamila S. De A. Tetrahedron 2003, 59: 4767

<A NAME="RU25005ST-8">8</A> Allen D. Callaghan O. Cordier FL. Dobson DR. Harris JR. Hotten TM. Owton WM. Rathmell RE. Wood VA. Tetrahedron Lett. 2004, 45: 9645

<A NAME="RU25005ST-9">9</A> Owton WM. Tetrahedron Lett. 2003, 44: 7147

<A NAME="RU25005ST-10">10</A> Ho J.-H. Ho T.-I. Tetrahedron Lett. 2003, 44: 4669

<A NAME="RU25005ST-11">11</A> Cabiddu MG. Cabiddu S. Cadoni E. Demontis S. Fattuoni C. Melis S. Tetrahedron 2002, 58: 4529

<A NAME="RU25005ST-12">12</A> Kim P. Tsuruda JM. Olmstead MM. Eisenberg S. Kurth MJ. Tetrahedron Lett. 2002, 43: 3963

<A NAME="RU25005ST-13">13</A> Katritzky AR. Vvedensky VY. Tymoshenko DO. J. Chem. Soc., Perkin Trans. 1 2001, 2483

<A NAME="RU25005ST-14">14</A> Larock RC. Yue D. Tetrahedron Lett. 2001, 42: 6011

<A NAME="RU25005ST-15">15</A> Gallagher T. Pardoe DA. Porter RA. Tetrahedron Lett. 2000, 41: 5415

<A NAME="RU25005ST-16">16</A> Samanta SS. Ghosh SC. De A. J. Chem. Soc., Perkin Trans. 1 1997, 2683

Typical Procedure. A mixture of α-haloketone (1 mmol), arylthiol (1 mmol), Na₂CO₃/SiO₂ (1.0 g, 1.5 mmol) and PPA/SiO₂ (3.5 g, 10 wt%) in chlorobenzene (15 mL) was stirred at 135 °C for 6 h, and then used supported reagents were removed by filtration. The filtrate was evaporated to leave crude product, which was purified by flash column chromatography to give the desired product.

Preparation of Na ₂ CO ₃ /SiO ₂ .
Silica gel [Wakogel C-200 (Wako Pure Chemical Ind. LTD.), 16.82 g] was added to a solution of sodium carbonate (30 mmol, 3.18 g) in distilled H₂O, and the mixture was stirred at r.t. for 0.5 h. Then, H₂O was removed by rotary evaporator under reduced pressure, and the resulting reagent was dried in vacuo (10 mmHg) at 160 °C for 5 h.

Preparation of PPA/SiO ₂ .
The PPA (2.0 g) and CHCl₃ (100 mL) were placed in a round-bottom flask, and the mixture was stirred at 50 °C for 1 h. SiO₂ [Wakogel C-200 (Wako Pure Chemical Ind. Ltd.), 18.0 g], which was dried in vacuo at 160 °C for 2 h, was added to the mixture, and the mixture was stirred for another 1 h. Then, CHCl₃ was removed with rotary evaporator and the resulting solid was dried in vacuo at r.t. for 3 h.

Compound 3b: mp 46-47 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.33 (3 H, s), 2.46 (3 H, s), 4.17 (2 H, s), 7.09 (1 H, d, J = 8.3 Hz), 7.18-7.29 (5 H, m), 7.42 (1 H, s), 7.59 (1 H, d, J = 8.3 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 11.7, 21.5, 34.4, 121.5, 121.8, 125.4, 126.4, 127.3, 128.4, 128.5, 133.5, 135.7, 137.7, 139.8, 141.1. HRMS (TOF-CI): m/z calcd for C₁₇H₁₇S [MH⁺]: 253.1050; found: 253.1056.
Compound 3d: mp 60-61 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.36 (3 H, s), 2.47 (3 H, s), 4.20 (2 H, s), 7.07 (1 H, d, J = 7.3 Hz), 7.18-7.30 (6 H, m), 7.48 (1 H, d, J = 7.6 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 11.9, 20.2, 34.4, 119.1, 124.1, 124.3, 126.4, 128.3, 128.5, 128.5, 131.6, 137.2, 138.7, 139.8, 140.7. HRMS (TOF-CI): m/z calcd for C₁₇H₁₇S [MH⁺]: 253.1050; found: 253.1044.
Compound 3e: ¹H NMR (400 MHz, CDCl₃): δ = 2.33 (3 H, s), 4.19 (2 H, s), 7.21-7.32 (5 H, m), 7.36 (1 H, dd, J = 8.5, 2.0 Hz), 7.56 (1 H, d, J = 8.5 Hz), 7.76 (1 H, d, J = 2.0 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 11.7, 34.4, 118.0, 123.5, 124.3, 126.6, 126.6, 127.0, 128.5, 128.6, 137.2, 139.3, 139.9, 142.6. HRMS (EI): m/z calcd for C₁₆H₁₃BrS [M⁺]: 315.9921; found: 315.9922.
Compound 3f: ¹H NMR (400 MHz, CDCl₃): δ = 2.33 (3 H, s), 3.88 (3 H, s), 4.18 (2 H, s), 6.92 (1 H, dd, J = 8.8, 2.4 Hz), 7.08 (1 H, d, J = 2.4 Hz), 7.21-7.31 (5 H, m), 7.59 (1 H, d, J = 8.8 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 11.8, 34.5, 55.6, 104.3, 113.4, 122.8, 126.5, 127.4, 128.4, 128.5, 130.9, 139.1, 139.7, 141.9, 157.4. HRMS (TOF-CI): m/z calcd for C₁₇H₁₇OS [MH⁺]: 269.1000; found: 269.1001.
Compound 3g: mp 98-100 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.80 (3 H, s), 4.30 (2 H, s), 7.20-7.32 (5 H, m), 7.48-7.59 (2 H, m), 7.65 (1 H, d, J = 8.8 Hz), 7.75 (1 H, d, J = 8.8 Hz), 7.93 (1 H, dd, J = 8.0, 1.2 Hz), 8.71 (1 H, d, J = 8.5 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 16.9, 34.5, 120.7, 123.3, 124.5, 124.7, 125.8, 126.5, 128.4, 128.6, 129.0, 130.4, 130.5, 132.1, 134.7, 136.5, 137.5, 139.8. HRMS (TOF-CI): m/z calcd for C₂₀H₁₇S [MH⁺]: 289.1050; found: 289.1049.
Compound 3k: mp 103-104 °C. ¹H NMR (400 MHz, CDCl₃): δ = 1.24 (3 H, t, J = 7.1 Hz), 4.22 (2 H, q, J = 7.1 Hz), 4.29 (2 H, s), 7.41 (1 H, s), 7.50-7.62 (2 H, m), 7.72 (1 H, d, J = 8.7 Hz), 7.85 (1 H, d, J = 8.7 Hz), 7.95 (1 H, dd, J = 8.0, 1.2 Hz), 8.43 (1 H, d, J = 8.3 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 14.1, 38.4, 61.1, 121.1, 122.9, 124.9, 125.3, 125.7, 126.2, 129.0, 129.9, 130.8, 131.9, 132.8, 139.4, 170.9. HRMS (TOF-CI): m/z calcd for C₁₆H₁₅O₂S [MH⁺]: 271.0792; found: 271.0798.
Compound 3m: mp 166-168 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.15-7.29 (6 H, m), 7.36-7.45 (6 H, m), 7.51 (1 H, d, J = 8.5 Hz), 7.75 (1 H, d, J = 8.8 Hz), 7.89 (2 H, d, J = 8.5 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 120.4, 123.7, 124.8, 125.6, 125.7, 127.4, 127.8, 128.2, 128.8, 128.9, 129.7, 130.1, 130.8, 132.2, 134.5, 134.5, 135.7, 137.1, 138.3, 139.9. HRMS (TOF-CI): m/z calcd for C₂₄H₁₇S [MH⁺]: 337.1050; found: 337.1045.